Newsletter III /2018... · Topic: Microencapsulation of reactive components Date: 24th of October...

Newsletter III /2018

Microcapsulation for Personal Care

Applications

Newsletter III/2018 © Fraunhofer IAP © Fraunhofer ICT

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0. TPM members’ corner ............................................................................................................... 3

I . In Focus: “Microencapsulation for Personal care Applications” ...................................... 4

Introduction ......................................................................................................................... 4 I.1

Patent evaluation ................................................................................................................ 4 I.2

I.2.1 Search strategy ................................................................................................................. 4 I.2.2 Evaluation of patents ........................................................................................................ 5 I.2.3 Patent highlights............................................................................................................. 11

Literature evaluation .........................................................................................................15 I.3

I.3.1 Search strategy and statistics .......................................................................................... 15 I.3.2 Details ............................................................................................................................ 15

I.3.2.1 Leon 2017 (Firmenich): Formaldehyde-free melamine microcapsules as core/shell delivery systems for encapsulation of volatile active ingredients .............................. 15 I.3.2.2 Kaur 2018: Potential use of polymers and their complexes as media for storage and delivery of fragrances ............................................................................................. 16 I.3.2.3 Martins 2017: Oil encapsulation techniques using alginate as encapsulating agent: applications and drawbacks .................................................................................... 17 I.3.2.4 Costa 2017: Delivery systems for cosmetics - From manufacturing to the skin of natural antioxidants ................................................................................................ 20

FROST & SULLIVAN Market studies and insigths .........................................................21 I.4

I.4.1 Advancements in Materials for Personal Protection, Cosmetic Delivery, Printing, and Corrosion Protection ....................................................................................................... 21 I.4.2 Innovations in Natural Protein-based Delivery Systems for Flavors ................................... 21 I.4.3 Materials and Process Innovations for Microencapsulation Technologies ......................... 23 I.4.4 Breakthrough Delivery Technologies For Flavors And Fragrances ..................................... 23

Summary ..........................................................................................................................24 I.5

Literature ...........................................................................................................................25 I.6

I I . Information platforms and interesting news .............................................................26

Regularly updated information platforms ........................................................................26 II.1

Interesting news, projects and publications ....................................................................26 II.2

II.2.1 Interesting news and projects ......................................................................................... 26

II.2.1.1 Microplastics and synthetic polymers in cosmetic products and washing and cleaning preparations ............................................................................................. 26 II.2.1.2 Intentionally added microplastics in products .......................................................... 27 II.2.1.3 Overview on joint projects on the subject of plastic in the environment .................. 27

II.2.2 New publications ......................................................................................................... 28

Upcoming events ..............................................................................................................29 II.3

Contents


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(1) TPM Calendar 2018

Literature and patent updates: calendar week 9, 18, 26, 35, 44 / 2018; 1 / 2019

Newsletters: calendar week 26, 38, 51 / 2018

TPM Meeting: 21st of March 2018 (location: Fraunhofer Institute for Silicate Research

ISC, Würzburg)

Preparation of TPM workshop 2019 (Topic, date, location – see below)

(2) Newsletter Topics 2018-2019

Ranking Topic Release

1 Trends in microencapsulation 2017/18 updated published

2 Microcapsules for paint applications published

3 Microencapsulation for personal care applications this newsletter

4 Encapsulation of solid materials ca. KW13/2019

5 Microencapsulation for agrochemical ca. KW38/2019

6 Microcapsules for textile applications ca. KW51/2019

(3) TPM Homepage

The homepage is online: http://www.platform-microencapsulation.fraunhofer.de

Some TPM members have offered to present their activities in the field of microencapsulation

on the homepage. Currently we are preparing a template. We will provide you with

further information by the beginning of 2019.

Furthermore, please send us your proposals regarding the content of the homepage.

(4) Workshop 2019

Topic: Microencapsulation of reactive components

Date: 24th of October 2019 (Pls. save the date)

Location: Fraunhofer Institute for Manufacturing Technology and Advanced Materials

IFAM in Bremen / Germany

You are invited to give a presentation and/or propose a lecturer. Please let us know

your proposals until the end of January 2019.

0. TPM members’ corner

http://www.platform-microencapsulation.fraunhofer.de/


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The first question to answer is what personal care applications are. People often use the term "personal care products" to refer to a wide variety of items that commonly can be found in the health and beauty sections of drug and department stores. According to WIKIPEDIA “Personal care (or toiletries) are consumer products used in personal hygiene and for beautification”. Ingredients of personal care products are antimicrobials, colorants, conditioning polymers, emollients, emulsifiers, surfactants, UV absorbers and many more. From the perspective of microencapsulation, fragrance, as an important kind of addition, has been applied widely in personal care applications. This trend has been rising in recent years. For fragrances, one of the main interests is to improve the delivery of imparted fragrant molecules with controlled release and long life because most fragrance delivery systems have the drawbacks of premature evaporation and degradation during storage. Fragrance chemicals are added in various products, such (laundry) detergents, fabric softeners, soaps, and personal care products (e.g. shampoos, body washes, deodorants). The aroma present in these compounds provokes and induces a pleasurable sensation to uplift emotional levels. (Kaur 2018) Companies active in personal care are mostly suppliers of ingredients, raw materials, packaging and/or manufacturers and distributors of finished products. Microencapsulation is carried out both by the manufacturers of materials and by the manufacturers of finished products. For the identification of current trends in personal care applications in connection with microencapsulation, patents as well as scientific articles were evaluated in the period 2017- 2018.

I.2.1 Search strategy

Patent data are retrieved from PatBase (www.patbase.com). PatBase is a database which uses patent families as units. The patent family is defined as a collection of patents which have the same claims but are registered in different countries. This reduces the risk of counting the same inventions multiple times for patent statistics.

The patent search was carried out using the search word combinations listed below (last retrieval 03.10.2018). The search was performed in the patent title (T), abstract (A) and claims (C). Search 1: TAC= (microcapsul* or nanocapsul* or microencapsul* or nanoencapsul*) (Results 34749) Search 2: TAC= ("personal care") (Results 6936) Search 3: TAC= (toiletry or toiletries) (Results 5489) Search 4: 2 or 3 (Results 12328) Search 5: 1 and 4 (Results 185)

I . In Focus: “Microencapsulation for Personal care Applications”

Introduction I.1

Patent evaluation I.2


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Patents published from 2017 were evaluated in terms of technical details as well as bibliographic data. Detailed information about interesting patent applications (from our point of view) are provided in the following sections.

I.2.2 Evaluation of patents

The patents identified in search 5 were evaluated according the patent focus (“approach, advantage, novelty”). Patents which may be useful for the TPM members are shown in Tab. 1. A list of all relevant patents and the complete search results can be supplied on demand.

Tab. 1 Microencapsulation for personal care applications – list of useful patents (marked in green: two patent assignees, assignees in alphabetical order)

Patent number Nr. of Patents in Family

Title Assignee Approach/advantage/novelty

WO2017089116 WO2017089115 9 applications

MICROCAPSULE COMPRISING A POLYESTER-URETHANE SHELL AND A HYDROPHOBIC CORE MATERIAL

BASF SE polyester-urethane shell microcapsules with improved properties and biodegradable segments embeded in the capsule wall

WO2017085033 2 applications See also: WO2017085105

IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS

BASF SE GIVAUDAN SA

positive charged microcapsule shell based on polyurea which contains permanent cationic groups covalently bonded to the shell (core component not containing a fragrance GIVAUDAN patent)

US2017326522 (WO2016071152) US2017354945 (WO2016071153) 4 applications

PROCESS FOR PREPARING MICROCAPSULES HAVING A POLYUREA SHELL AND A LIPOPHILIC CORE MATERIAL

BASF SE polyurea microcapsules having enhanced stability against leacking-out of the core components (core component not containing a fragrance)

US2017283735 (US2017283736, US2017281985, US2017281986, US2016106635, US2016108339, US2016108340, WO2016061435, WO2016061439, WO2016061440) See also: US2017216161, US2017216162, US2017216163 19 applications

CONTROLLED RELEASE DUAL WALLED MICROCAPSULES

ENCAPSYS LLC PROCTER & GAMBLE

method of forming dual melamine/acrylic walled microcapsules having improved physical properties and release control

US2017002293 (WO2017004338,

COMPOSITIONS CONTAINING

ENCAPSYS LLC ; PROCTER AND GAMBLE

personal care composition providing multiple blooms of


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WO2017004339, WO2017004340, WO2017004343, US2017002301, US2017002302, US2018110700) 17 applications

MULTIPLE POPULATIONS OF MICROCAPSULES

fragrance, the multiple blooms being provided for by different populations of microcapsules

WO2018115250 1 application

DENSITY BALANCED HIGH IMPACT PERFUME MICROCAPSULES

FIRMENICH AND CIE oil-based core comprises a perfume oil having high impact perfume raw materials and a density balancing material


MICROCAPSULES HAVING A MINERAL LAYER

FIRMENICH AND CIE a polymeric shell having a terminating charged functional surface; and a mineral layer on the terminating charged functional surface


HYBRID MICROCAPSULES

FIRMENICH AND CIE formaldehyde-free organic-inorganic microcapsules


PROCESS FOR THE PREPARATION OF MICROCAPSULES

FIRMENICH AND CIE preparation of melamine- formaldehyde free microcapsules: poly(urea-urethane) capsule walls



FIRMENICH AND CIE poly(urea-urethane) capsule wall, free of formaldehyde, mean diameter (d(v, 0.5)) > 500 μm, ionic emulsifier in the aqueous phase such as gum Arabic, soy protein, sodium caseinate, gelatin, bovine serum albumin, sugar beet pectin, hydrolyzed soy protein, co-polymers of acrylamide and acrylic acid etc.



FIRMENICH AND CIE polyurea-based capsules prepared by simplified and cost-effective processes


CORE-COMPOSITE SHELL MICROCAPSULES

FIRMENICH AND CIE outer shell by coacervation surrounding an hydrophobic active ingredient (internal phase); and an inner shell by interfacial polymerization at the interface between the internal phase and the outer shell

WO2017102812 4 applications

PROCESS FOR PREPARING POLYUREA MICROCAPSULES WITH IMPROVED DEPOSITION

FIRMENICH AND CIE process for producing perfume- or flavor- containing polyurea microcapsules with improved deposition of encapsulated actives on targeted surfaces

US2018178183 (WO2017001385) 6 applications

DELIVERY SYSTEM WITH IMPROVED DEPOSITION

FIRMENICH AND CIE microcapsules coated by a particular mixture of copolymers, which demonstrate a high rate of deposition when applied on a substrate


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PROCESS FOR PREPARING POLYUREA MICROCAPSULES

FIRMENICH AND CIE perfume-containing microcapsules with improved olfactive performance by using at least one aromatic polyisocyanate with a specific mixture of polyamines


PROCESS FOR THE PREPARATION OF MICROCAPSULES FREE FROM MELAMINE-FORMALDEHYDE

FIRMENICH AND CIE to a new process for the preparation of melamine-formaldehyde free microcapsules (poly(urea-urethane))


MICROCAPSULES WITH HIGH DEPOSITION ON SURFACES

FIRMENICH SA microcapsules formed by interfacial polymerization, which present high deposition properties (poly(urea-urethane))


HYBRID PERFUME MICROCAPSULES

FIRMENICH SA organic-inorganic hybrid core-shell microcapsules having a shell made from the hydrolysis and condensation reaction of particular polyalkoxysilane macro-monomeric compositions


PROCESS FOR PREPARING ANTIMICROBIAL MICROCAPSULES

FIRMENICH SA polyurea core-shell microcapsules with immobilized silver particles into and onto the shell


PROCESS FOR PREPARING POLYUREA MICROCAPSULES WITH IMPROVED DEPOSITION

FIRMENICH SA

improved deposition of encapsulated actives on targeted surfaces


PERFUME COMPOSITIONS

GIVAUDAN SA improved balance between storage stability in consumer products and perfume diffusivity from intact microcapsules deposited on substrates


IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS

GIVAUDAN SA the capsule shell (a reaction product of at least one at least difunctional anionically modified isocyanate with an amine or alcohol, preferably a polyamine) is formed around droplet of core material that is stabilized with a positively charged colloidal stabilizer


MICROCAPSULES GIVAUDAN SA improved perfume-containing aminoplast microcapsule not prone to discoloration (shell crosslinked with diamine instead of resorcinol)


IMPROVEMENTS IN OR RELATING TO ENCAPSULATED PERFUME

GIVAUDAN SA a positive charge bearing perfume-containing aminoplast core-shell microcapsule synthesized by replacing the conventional anionic sulphonate-containing polymeric


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COMPOSITIONS stabilizer, with an alternative polymer bearing polyatomic cations

The following 5 patents of applicant INT FLAVORS & FRAGRANCES INC belong to the same patent family!

US2018015009 (comp. WO2018053356) 22 applications

MICROCAPSULE COMPOSITIONS WITH IMPROVED DEPOSITION

INT FLAVORS & FRAGRANCES INC

positively charged polyurea or polyurethane capsules having a zeta potential of 10 mV or greater by using a copolymer of acrylamide and acrylamidopropyltrimonium chloride as a deposition aid


MICROCAPSULE COMPOSITIONS STABILIZED WITH VISCOSITY CONTROL AGENTS


microcapsule compositions each comprising a microcapsule suspended in an aqueous phase and a viscosity control agent, wherein the viscosity control agent is an acrylate copolymer, a cationic acrylamide copolymer, or a polysaccharide

US2017333863 (WO2017143174, WO2018053356) 22 applications

ENCAPSULATED ACTIVE MATERIALS


encapsulating polymer comprises a polyisocyanate wherein the polyisocyanate is the reaction product of polymerisation between at least one polyisocyanate, a crosslinking agent and at least one additional polymer

US2017333863 22 applications

ENCAPSULATED ACTIVE MATERIALS


polyurethane and polyurea microcapsules that may be modified with additional polymers

US2017252274 22 applications

POLYUREA CAPSULES PREPARED WITH ALIPHATIC ISOCYANATES AND AMINES


polyurea capsules resulting from the polymerization of an aliphatic polyisocyanate and a cross-linking agent such as a diamine, amphoteric amine or guanidine amine/salt


STABLE MICROCAPSULE COMPOSITIONS

INT FLAVORS AND FRAGRANCES INC

microcapsule dispersed in an aqueous phase and a stabilizing agent (a combination of a negatively charged clay and a cationic polymer)


RELOADABLE MICROCAPSULES


microcapsule core contains a hydrophobic core solvent and a hydrophilic core solvent, and the microcapsule wall, formed of an encapsulating polymer, is permeable to the hydrophilic core solvent

US2018042825 MICROCAPSULE INT FLAVORS AND a microcapsule composition which


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(WO2016144798) 4 applications

COMPOSITIONS WITH HIGH PERFORMANCE

FRAGRANCES INC contains a polyurea or polyurethane microcapsule, an alkylnaphthalenesulfonate formaldehyde condensate, and polyvinylpyrrolidone

US2018021241 1 application

HYDROGEL CAPSULES AND PROCESS FOR PREPARING THE SAME


a hydrogel capsule (based on polymerized acrylic or methacrylic acid, or ester thereof) with a fragrance encapsulated therein during the polymerization process


FRIABLE SHELL MICROCAPSULES, PROCESS FOR PREPARING THE SAME AND METHOD OF USE THEREOF

ISP INVESTMENTS LLC shell formed from oil-in-water emulsion polymerisation of monomer mixture consisting essentially of greater than 70 % by weight of at least one polyfunctional ethylenically unsaturated monomer, about 1 to about 30 % by weight of at least one unsaturated carboxylic acid monomer or its ester, and about 0 to about 30 % by weight of at least one vinyl monomer


RUPTURE RELEASE MICROCAPSULE FOR SKIN CARE APPLICATIONS

KIMBERLY CLARK CORP crosslinked biocompatible material comprising gelatin and a polyphenol wherein said crosslinked biocompatible material encapsulates and controllably releases hydrophobic, oil-soluble actives


COMPOSITIONS PROVIDING DELAYED RELEASE OF ACTIVES

NOXELL CORP ; PROCTER AND GAMBLE; LEEDS UNIV

coated microcapsules, said coated microcapsules including a polymeric shell and a liquid core material encapsulated therein; and a metallic coating surrounding said microcapsules


Consumer Product Compositions Comprising Microcapsules

PROCTER & GAMBLE deposition polymer disposed on an outer surface of the microcapsule (polyacrylate shell/ benefit agent core)

US2018235893 (WO2017074997, WO2017074995, US2017113200) 8 applications

ENCAPSULATION PROCTER & GAMBLE CO ENCAPSYS LLC

microcapsules having surface charge helps to improve deposition of the microcapsules on substrates such as textiles, skin, hair, fibers, or other surfaces and adhesion of microcapsules on surfaces such as foam or bedding material


MICROCAPSULES FORMED FROM PHOSPHATE ESTERS AND COMPOSITIONS

PROCTER AND GAMBLE CO

Water insoluble microcapsules formed of a phosphate ester and a multivalent ion


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CONTAINING SAME


PERSONAL CARE COMPOSITIONS


personal care composition includes a structured cleansing phase; a benefit phase including triglycerides, a cationic deposition polymer, and anionic microcapsules

US2015374593 (WO2016003947, US2017128333, US2017296449), US2015374609 (WO2016003948) 7 applications

PERSONAL CARE COMPOSITIONS AND METHODS


methods of enhancing the efficacy of microcapsules in personal care compositions


NANO-ENCAPSULATION USING GRAS MATERIALS AND APPLICATIONS THEREOF

TRUSTEES OF PRINCETION UNIV

compositions fabricated by flash nanoprecipitation (FNP) and, in particular, to nanoparticle compositions employing generally recognized as safe (GRAS) materials

WO2017108376 WO2017107889 5 applications

MICROCAPSULE UNILEVER NV microcapsule comprising a benefit agent inside a water insoluble porous inner shell, an outer shell comprising at least one layer of cationic polymer and at least one layer of anionic polymer, and a non-ionic polysaccharide deposition aid

The patents reflect current trends and/or improvements in the handling, use and/or

formulation of the microcapsules for personal care products. This applies in particular:

1. The improvement of MICs dispersion stability (prevention of phase separation,

sedimentation, flotation etc.), e.g. by improvement of MICs density

(WO2018115250) and application of stabilizing agents in combination with

controlled capsule size and percentage of shell weight (US2017326522,

US2018169603).

2. Hybrid MIC shells, e.g. polymeric shell + mineral or metallic layer (WO2018115330,

WO2018054719, WO2016100477, WO2016100492, WO2015197757,

US2017142974) or other composite MIC shells besides the hybrid shell:

WO2018002214

3. Dual walled microcapsules besides hybrid dual walled microcapsules (WO2016061435, WO2016061439, WO2016061440)

4. Improved deposition of microcapsules on targeted surfaces such as fiber, hair and

skin (WO2018115330, WO2018169898, US2018015009, WO2017085033,

WO2017102812, WO2017001385, WO2017074995,WO2017074997,


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WO2016193435, WO2015189309, WO2018050914, US2018015009,

WO2018114746A1)

5. Reloadable microcapsules: US2018064615

6. Preparation of formaldehyde free microcapsules (WO18054719, WO201801990,

WO2016116604, EP3031496, WO2018019908, WO2018019896, US2018112152)

7. Biocompatible and/or biodegradable and/or GRAS MICs (WO2017131644,

WO2017027474, WO2017089116)

8. Improvement of state-of-the-art microcapsules for different applications:

US2018185808, US2017333863, US2017333863, US2017252274, US2018042825,

US2018021241, WO2017123965, US2017191001

I.2.3 Patent highlights

I. Completely or partially biodegradable microcapsule walls / eco-friendly materials WO2017089116:

In a special embodiment of this invention the polymeric shell material shows biodegradability.

The biodegradable poly(ester-urethane) shell material is prepared by reacting at least one polycaprolactonediol or a polylactonetriol having a number-average molecular weight of from 250 to 3000 g/mol with at least one polyisocyanate containing at least 2 NCO groups.

WO2018019908:

It is stated that capsules such as aminoplast ones suffer from stability problems when used in consumer products comprising surfactants, especially after prolonged storage at elevated temperatures.

The encapsulated active tends to leak out of the capsule by diffusion through the wall due to the presence of surfactants that are able to solubilise the encapsulated active in the product base.

The inventors propose poly(urea-urethane) capsule walls combining an anionic bio-sourced polyol (lignin, lignin sulfate, carboxymethyl cellulose, alginic acid sodium salt, polygalacuronic acid, dextran sulphate sodium salt and mixtures thereof) with a specific protic acid catalyst. Only specific acids allowed obtaining capsules with the desired stability, e.g. glyoxylic acid, citric acid, tartaric acid, fumaric acid, salicylic acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, chlorhydric acid, malic acid, lactic acid, oxalic acid and mixtures thereof.

Description of the term “Biodegradation”: In WO2017089116 the term biodegradation is described as follows: “…..the polymers decompose in an appropriate and demonstrable period of time when exposed to the effects of the environment. The degradation mechanism can be hydrolytic and/or oxidative, and is based mainly on exposure to microorganisms, such as bacteria, yeasts, fungi, and algae.” Methods proposed for determining biodegradability are:

ASTM D5338, ASTM D6400, EN 13432, and DIN V 54900: Mixing of the polymer with compost and storing the mix for a particular time. “The biodegradability is


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defined here by way of the ratio of the netto amount of CO2 liberated from the specimen (after deducting the amount of CO2 liberated by the compost without the specimen) to the maximum possible amount of CO2 liberated by the specimen (calculated from the carbon content of the specimen). Even after a few days of composting, biodegradable polymers generally show marked signs of degradation, for example fungal growth, cracking, and perforation.”

Y. Tokiwa et al., American Chemical Society Symposium 1990, Chapter 12, "Biodegradation of Synthetic Polymers Containing Ester Bonds": The polymer is incubated with a certain amount of a suitable enzyme at a certain temperature for a defined period, and then the concentration of the organic degradation products dissolved in the incubation medium is determined. For the purposes of WO2017089116, biodegradable polymers are those “…which after enzymatic treatment with a lipase from Rhizopus arrhizus for 16 h at 35 °C give a DOC value which is at least 10 times higher than that for the same polymer which has not been treated with the enzyme.”

II. Dual wall / multi-layered microcapsules / hybrid microcapsules US2017283735:

Improved dual melamine resin/-(meth)acrylate polymer walled microcapsules with two discrete layers.

Combination of (a) at least one oil soluble or dispersible amine (meth)acrylate, (b) at least one oil soluble or dispersible acidic (meth)acrylate or at least one oil soluble or dispersible simple acid or both, and (c) at least one oil soluble or dispersible multifunctional (meth)acrylate monomer or oligomer in forming the (meth)acrylate ester-based portion of the microcapsule wall.

WO2018115330:

Improved deposition on a substrate and adherence on the substrate for leave-on and rinse-off applications.

Mineral layer onto a terminating charged surface of the microcapsule.

The mineral layer does not comprise silicon oxides.

Various shell materials such as polyurea. These microcapsules were then surface-modified with alternating polyelectrolyte multilayers prior to adsorption and hydrolysis of mineral precursors.

WO2018054719:

Formaldehyde-free organic-inorganic microcapsule.

The polymeric shell comprises inorganic particles with non-chemically surface modification.

Pickering emulsion process / Interfacial polymerization / Polyurea/Polyurethane

WO2018002214:

Perfume capsules with a composite wall can be formed by polymerisation of a polyisocyanate in absence of a reactant such as an amine or polyamine into an existing coacervate shell.

These capsules demonstrate a high performance in terms of stability.

The coacervate shell is made from gelatin and a second polyelectrolyte (e.g. carboxymethyl cellulose, sodium carboxymethyl guar gum, xanthan gum and plant gums such as acacia gum).


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US2017137757:

The inventors describe stable core-shell microcapsules having a wall made from the hydrolysis and condensation reaction of a particular polyalkoxysilane macro-monomeric composition (organic-inorganic hybrid wall).

Said composition can be introduced or prepared in situ in the oil phase during the process of preparation of the microcapsules.

The core-shell microcapsules present very high perfume retention and improved mechanical properties.

US2017142974:

The formation of silver particles during the interfacial polymerization conducted in the presence of an anionic emulsifier is described.

The process leads to microcapsules able to deliver active ingredients, such as perfumes together with antimicrobial agents while reducing the amount of free particles in solution.

III. Improved deposition on microcapsules on targeted surfaces (fiber, hair, skin, furniture, floor, fabric) WO2017102812:

The approach combines the use of a specific emulsifier together with that of the use of a polymeric cross-linker to generate aggregated droplets stabilized by the emulsifier of the invention.

The addition at the end of the process of a polyamine triggers the interfacial polymerization leading to a core-shell capsules that are at least partly aggregated and with surface property favoring the deposition on the surface such as fiber, hair and skin.

A significant improvement of deposition over the known partly aggregated capsules obtained by using a polymeric cross-linker, is observed only by the combination of both features; i.e. a specific emulsifier and the polymeric cross- linker.

US2018178183:

The microcapsules having an oil-based core and a polymeric shell are coated with a composition comprising at least a first cationic copolymer and a second cationic polymer.

Specific compositions containing at least two different cationic polymers present in specific ratios, could significantly improve the performance of those microcapsules in terms of deposition and long lasting effect of the active ingredient encapsulated therein.

US2018078468:

The invention provides microcapsules with boosted deposition properties by association of cationic deposition-promoting aids with an emulsifier consisting of an anionic or amphiphilic biopolymer in particular ratios.

The polymeric shell is formed by interfacial polymerisation in the presence of an anionic or amphiphilic biopolymer followed by a coating comprising a cationic polymer.


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WO2018050914:

By introducing a positively charged species as a colloidal stabilizer into an aqueous phase prior to emulsification and before microcapsule formation, it is possible to incorporate a positive charge into the shell that remained substantially constant and is not washed out during capsule formation, or subsequently during storage and use.

This could be achieved without negatively affecting the physical stability of the microcapsule or its olfactive performance.

The positively charged shell is a reaction product of at least one at least difunctional anionically modified polyisocyanate with amines, preferably with polyamines, in the presence of a positively charged colloidal stabilizer.

IV. Reloadable microcapsules US2018064615:

A microcapsule suitable for encapsulating fragrances having ingredients that either have high water solubility or are reactive towards wall-forming materials.

Microcapsules bearing a sacrificial hydrophilic core solvent (e.g. triethyl citrate, triacetin, benzyl acetate, ethyl acetate, propylene glycol, dipropylene glycol, glycol ethers, and combinations thereof) and/or a hydrophobic core solvent (e.g. isopropyl myristate, C5-C50 (e.g., C5-C20 and C6-C15) tryglyceride (e.g., caprylic triglyceride, capric triglyceride, and a mixture thereof), D-limonene, silicone oil, mineral oil, and combinations thereof) are developed.

The active material is initially outside of the microcapsule wall.

The microcapsule wall is permeable to the core solvent and the active material.


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I.3.1 Search strategy and statistics

Relevant scientific articles searched using the Web of Science (apps.webofknowledge.com, last access 10.11.2018). The articles are searched for

TOPIC: (microcapsul* OR microencapsul*)

Refined by TOPIC: (personal care)

PUBLICATION YEARS: (2017 OR 2018)

About 80 % of the hits are patents (comp. section I.2). The remaining articles are evaluated. Relevant and interesting details are presented in section I.3.2.

I.3.2 Details

I.3.2.1 Leon 2017 (Firmenich): Formaldehyde-free melamine microcapsules as core/shell delivery systems for encapsulation of volatile active ingredients

In the article, the authors propose a formaldehyde-free solution based on dialdehydes, and in particular glyoxal. The authors found that

The presence of glyoxal (a precursor of DME) is necessary to obtain a good cross- linking between amines and aldehydes.

The presence of 2,2-dimethoxyethanal (DME) gives good conversion to the resins.

A mixture of model fragrance compounds was encapsulated applying the formaldehyde-free melamine resins. The hermeticity of the microcapsules was determined using thermogravimetric analyses. The mass loss was estimated over the time. The capsules with the lowest leakage were those prepared with glyoxal/DME molar ratios at 4 and 6. But none of the capsules was completely hermetic. Therefore, additional cross-linking of the microcapsules was performed to improve the hermeticity by:

a. Addition of a solution of urea or guanazole (GZ) in the dispersion of capsules before the last step of the process to cross-link oligomers inside the shell.

b. Addition of hexamethylenediisocyanate (HDI, dissolved in the oil phase) to react with the amino groups

Some results of the optimization experiments are shown in Table 2:

Literature evaluation I.3


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Tab. 2 Influence of different cross-linking agents on the hermeticity of model fragrance (GZ guanazole, HDI hexamethylenediisocyanate)

By addition or urea or GZ, a significant decrease of the mass loss was measured. These results confirm that an excess of amines, urea or guanazole, favors the cross-linking in the shell. The authors assume that this reaction reduces the porosity of the capsule wall. In the presence of HDI, the cross-linking reaction between the amino groups of the resin and the isocyanate functions take place at the oil/water interface with a hermetic capsule as the results at appropriate HDI concentrations. Concerning the mechanical stability, the HDI cross-linked capsules show the best performance. The mechanical measurements reveal an interesting combination of robustness and breakability.

I.3.2.2 Kaur 2018: Potential use of polymers and their complexes as media for storage and delivery of fragrances

In this article, current applications of various polymers and their complexes in fragrance delivery systems are briefly reviewed. Functionality and applicability of these polymers are highlighted in order to provide a comprehensive view on the development of these materials in perfume industry. The authors focus on the following points:

1. Materials for encapsulation (polymers, biomolecules, porous materials; comp. figure 1) 2. Types of fragrances loaded (esters, terpenes, alcohols, aldehydes) 3. Performance of encapsulation materials and media 4. Critical assessment of polymeric materials in fragrance delivery 5. Microencapsulation of fragrances vs. pro-fragrances

The authors note that because of the complexity of the majority of the fragrances, the applicability of the pro-fragrance approach is restricted to specific types of chemicals. For this reason, microencapsulation technology is considered a more flexible method for the encapsulation of fragrances. A major area of research in fragrance delivery is to realize the development of low-cost fragrance carriers owing to limited profit margins in the highly competitive cosmetic industry. According to the authors, the low cost and ease of availability of natural polymers (such as


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polysaccharides) and zeolites (unit price: e.g.,<1 USD) as raw materials make them a preferred choice for microencapsulation and sustained release of fragrances.

Fig. 1 List of various materials used for encapsulation of fragrant molecules.

I.3.2.3 Martins 2017: Oil encapsulation techniques using alginate as encapsulating agent: applications and drawbacks

The focus of this publication is the microencapsulation of oils. The authors identified oils as compounds which are widely used in agricultural (pesticides), nutritional (vitamins, fish oil), foods (flavor, essential oils, lipids, dye) and cosmetics (vegetal oils, fragrance) industries. In cosmetic industries, oils are largely used due to their anti-oxidant, nourishing and moisturising properties. The encapsulation provides better protection of active compound and grants attractive visual aspect to final product. Encapsulated fragrances are frequently applied in perfumes, creams and other body care products; however, their application is not only restricted to cosmetic. A recent and promising segment of market has used encapsulated fragrances to aromatise environments and graphic materials with the finality to create a consumer olfactory memory. This concept consists in associating a trademark, logo, product or point of sale with a specific fragrance creating an olfactory identity that can be easily exploited as marketing strategy. An overview of the use of nano-, micro- and millicapsules in several industrial applications is given in figure 2. The article is dedicated in particular to the use of alginate as capsule wall material for encapsulation of oils because of their versatility with broad applications in several industrial fields. The main techniques used in oil encapsulation, spray-drying, dripping, dispersion and millifluidic are presented in more details (figures 3, 4).


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Fig. 2 Use of nano, micro and millicapsules in several industrial applications

Fig. 3 Techniques of oil encapsulation


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Fig. 4 Oil encapsulation with alginate by simple extrusion-dripping using external (A), internal (B) or inverse gelation (C) mechanism. Black arrows: direction of migration of Ca2+

In table 3, the techniques for oil encapsulation are compared regarding capsule and encapsulation technique characteristic.

Tab. 3 Comparison of the techniques of oil encapsulation based on production and physico-chemical properties of capsules criteria

Finally, the authors conclude, that the oil encapsulation market is actually boosted by the discovery of new vegetable oils with medicinal or cosmetic properties associated with the


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development of the encapsulation technologies. The combination of these two factors has opened the doors for the creation of more efficient and innovative products.

I.3.2.4 Costa 2017: Delivery systems for cosmetics - From manufacturing to the skin of natural antioxidants

This review article focuses on delivery systems in cosmetic products. Some of the delivery systems used in the cosmetic industry are described, some general considerations about their presence and incorporation in cosmetic formulations as well as their skin interactions are made. The review also covers the manufacturing process of a cosmetic cream formulation, including basic ingredients, natural antioxidants in particular. In addition, future perspectives, recent concerns, and further work regarding the cosmetic industry are also considered. According to European definition, cosmetics are “any substance or mixture intended to be placed in contact with the external parts of the human body or with the teeth and the mucous membranes of the oral cavity to clean them, change their appearance, protect them, keep them in good condition or correcting body odors.” Therefore, a wide variety of products are included in the cosmetic category: make-up powders, toilet soaps, perfumes, shower preparations, depilatories, deodorants and antiperspirants, products for external intimate hygiene, skin, hair, oral and nail care products. However, this definition is not universal. Some products that are considered as cosmetics in Europe (sunscreen products, anticavity toothpastes, antiperspirants, antidandruff preparations, skin protectants and hair restorers) may be classified as over-the-counter drugs in the USA since the cosmetic definition is somehow narrower. New concerns about environmental impact or animal welfare are emerging with respect to the cosmetic development, manufacturing and quality control. Therefore, natural antioxidant are of special interest because they

present health benefits such as anti-ageing, anti-inflammatory, anti-carcinogenic, and antimicrobial properties that potentiate their use in cosmetic products

can also be used as preservatives since they avoid the lipid oxidation that usually occurs in cosmetic products

On the other hand, antioxidants may have stability issues and difficulties in crossing the transdermal barrier. Delivery systems can be used to protect sensitive active ingredients from degradation and to grant a target and controlled release. Several types of delivery systems (e.g. liposomes, niosomes, transfersomes, lipid nanoparticles, polymeric microparticles and nanoparticles) have been used in cosmetic formulations. Skin interaction with the different delivery systems depends mostly on their size, flexibility and composition. Mechanical forces, pH, or temperature could be used as triggers to promote the liberation.


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https://ww2.frost.com/

I.4.1 Advancements in Materials for Personal Protection, Cosmetic Delivery, Printing, and Corrosion Protection

TechVision Opportunity Engines D737/9A Chemicals, Materials & Foods (12.10.2018) The increasing focus on non-toxic and environment friendly materials is one of the current topics. Tranzderm Solutions (www.transdermsolutions.com) developed Naturproz, a plant-based material for encapsulation and delivery systems (figure 5).

Fig. 5 Naturproz, a user-friendly protein for encapsulation

I.4.2 Innovations in Natural Protein-based Delivery Systems for Flavors

TechVision Opportunity Engines D737/8F Chemicals, Materials & Foods (27.07.2018) Plant, animal, and microbial proteins act not only as food ingredients but also as delivery systems to carry flavors, fragrances, and nutraceuticals, protecting the same from challenging environments such as pH, oxidation, and so on. Significant progress has been made in developing formulations for protein carriers. With competition coming from polysaccharides, starches, and lipids, proteins become extremely significant in this market due to the high nutritional properties in these materials. Plant and fungal proteins find much higher adoption than animal proteins due to ban of the latter in some regions. Owing to some of the aforementioned reasons the adoption of natural proteins as encapsulates have been very high especially in the food and cosmetic segments (figures 6, 7).

FROST & SULLIVAN Market studies and insigths I.4

https://ww2.frost.com/

http://www.transdermsolutions.com/


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Fig. 6 Development for natural proteins used for encapsulation of actives (patent literature)

Fig. 7 Markets for natural proteins


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I.4.3 Materials and Process Innovations for Microencapsulation Technologies

TechVision Opportunity Engines D737/8A Chemicals, Materials & Foods 22.06.2018 This article reports on inorganic microcapsules for cosmetic applications (figure 8).

Fig. 8 Inorganic microcapsules for cosmetic applications

I.4.4 Breakthrough Delivery Technologies For Flavors And Fragrances

TechVision Analysis D7EA Chemicals, Materials & Foods 29.09.2017 This research service titled “Breakthrough Delivery Technologies for Flavors and Fragrances” focuses on capturing recent innovations and developments with regard to encapsulation technologies used for delivery of flavors and fragrances. The research service includes a holistic analysis of the different processes used, which includes their technical capabilities, limitation factors affecting their adoption, and key stakeholders involved in technology adoption. Insights are provided on the road ahead for technology developers in this space. The encapsulation processes considered are segmented on the basis of the methods used, namely, physical, physio-chemical, and chemical processes. Only processes used for encapsulating flavor and fragrance compounds have been considered within the scope of this research (figure 9).


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Fig. 9 Encapsulated flavor and fragrance market

Microcapsules for personal care applications are focused in particular in the current patent literature. In scientific articles, this application of microcapsules plays a rather subordinate role. Regardless of this, comparable topics are addressed in both the patent literature and scientific articles:

Improvement of microcapsules dispersion stability in the final consumer product, i.e. prevention of phase separation, sedimentation, flotation etc.

Improvement of the hermeticity of microcapsules by dual walls (polymer/polymer as well as hybrid MIC shells, i.e. polymeric shell + mineral or metallic layer).

Improved deposition of microcapsules on targeted surfaces such as fiber, hair and skin and thus their reloadability.

Preparation of formaldehyde free microcapsules.

Preparation of biocompatible and/or biodegradable and/or GRAS microcapsules.

The ingredients most commonly used in microencapsulated form are fragrances. The trend to microencapsulate fragrances for personal care applications has been rising in recent years. The reason is to improve the delivery of fragrant molecules with controlled release and long life. Special requirements for the capsule walls result primarily from the presence of surfactants in the personal care products.

Summary I.5


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León G, Paret N, Fankhauser P, Grenno D, Erni P, Ouali L, et al. Formaldehyde-free melamine microcapsules as core/shell delivery systems for encapsulation of volatile active ingredients. RSC Advances. 2017;7(31):18962-75. Kaur R, Kukkar D, Bhardwaj SK, Kim K-H, Deep A.

Potential use of polymers and their complexes as media for storage and delivery of fragrances.

Journal of Controlled Release. 2018;285:81-95.

Martins E, Poncelet D, Renard D.

A novel method of oil encapsulation in core-shell alginate microcapsules by dispersion-inverse

gelation technique.

Reactive and Functional Polymers. 2017;114:49-57.

Costa R, Santos L.

Delivery systems for cosmetics - From manufacturing to the skin of natural antioxidants.

Powder Technology. 2017;322(Supplement C):402-16.

Other relevant publications / research work that were not considered in the newsletter

He L, Hu J, Deng W.

Preparation and application of flavor and fragrance capsules.

Polymer Chemistry. 2018;9(40):4926-46.

McClements DJ.

Delivery by Design (DbD): A Standardized Approach to the Development of Efficacious

Nanoparticle- and Microparticle-Based Delivery Systems.

Comprehensive Reviews in Food Science and Food Safety 2018;17(1):200-19.

Literature I.6


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http://bioencapsulation.net/ (Homepage of the Bioencapsulation Research Group BRG, with

Newsletters, Conference and workshop calendar and more – not only in the field of

bioencapsulation!)

http://nanoparticles.org/ (“The information resource for particle technology”)

http://www.specialchem4cosmetics.com (search term “microencapsulation” or similar

especially new patents in the cosmetic field)

http://www.specialchem4polymers.com (search term “microencapsulation” or similar

especially new patents in chemistry)

http://www.alibaba.com (search term “microencapsulation” or similar products, suppliers

and prices)

http://www.scirp.org/journal/jeas/ (open-access Journal of Encapsulation and Adsorption

Sciences (JEAS) launched in 2011 scientific and technological advances that cover basic

sciences, engineering aspects and applied technology of molecules encapsulation and

adsorption.

http://www.chemeurope.com/en/microencapsulation.html

Microencapsulation services, videos, white papers, events, publications in the field of

microencapsulation

II.2.1 Interesting news and projects

II.2.1.1 Microplastics and synthetic polymers in cosmetic products and washing and cleaning preparations

I I . Information platforms and interesting news

Regularly updated information platforms II.1

Interesting news, projects and publications II.2

http://bioencapsulation.net/

http://nanoparticles.org/

http://www.specialchem4cosmetics.com/

http://www.specialchem4polymers.com/

http://www.alibaba.com/

http://www.scirp.org/journal/jeas/

http://www.chemeurope.com/en/microencapsulation.html


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In September 2018, the Fraunhofer Institute UMSICHT published a study on the subject of "Microplastics and synthetic polymers in cosmetic products and washing and cleaning preparations”. The complete report is available here: https://www.nabu.de/imperia/md/content/nabude/konsumressourcenmuell/ 20181004_mikroplastikstudie.pdf

DOI 10.24406/UMSICHT-N-494063

II.2.1.2 Intentionally added microplastics in products

Final report of the European Commission (DG Environment) published in October 2017

Microcapsules are mentioned as a source of microplastics in various parts of the document. (Pls. use the keyword "capsul" in the document to find relevant pages)

II.2.1.3 Overview on joint projects on the subject of plastic in the environment

https://bmbf-plastik.de/liste-der-verbundprojekte

Microplastics of textile origin - A holistic view: Optimized processes and materials, material flows and environmental behavior ….and many other projects.

https://www.nabu.de/imperia/md/content/nabude/konsumressourcenmuell/

https://www.nabu.de/imperia/md/content/nabude/konsumressourcenmuell/


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II.2.2 New publications

Polymers for Food Applications Editor: Tomy J. Gutiérrez Springer International Publishing Print ISBN 978-3-319-94624-5 Online ISBN 978-3-319-94625-2 pp. 447-479 Pedro J. García-Moreno et al.: Biopolymers for the Nano-microencapsulation of Bioactive Ingredients by Electrohydrodynamic Processing Electrohydrodynamic processing, including electrospinning and electrospraying, is an emerging technique for the encapsulation of bioactive ingredients (e.g. omega-3, vitamins, antioxidants, probiotics) with interest for the functional food industry. This chapter presents the fundamentals of electrohydrodynamic processes for the production of nano-microstructures (fibers or capsules) loaded with bioactive compounds. Particularly, it focuses on the properties as well as electrospinning and electrospray processing of food-grade polymers. The physicochemical characteristics of the resulting nano-microencapsulates will also be discussed. Electrospun and electrospray food-grade polymers include biopolymers such as proteins (e.g. zein, gelatin, whey, casein, amaranth, soy, egg and fish protein) and polysaccharides (e.g. pullulan, dextran, chitosan, starch, alginate, cellulose, cyclodextrin, xanthan gum), as well as blends of biopolymers with biocompatible synthetic polymers (e.g. poly-vinyl alcohol).


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Event: 11th Microencapsulation Training School

Date: April 9-12, 2019

Location: Loughborough, U.K.

Information: http://bioencapsulation.net/2019-Loughborough-Microencapsulation-

Training-School/

Event: PARTEC - International Congress on Particle Technology

Date: April 9-11, 2019

Location: Nuremberg, Germany

Information: www.partec.info/en/congress-info/about-2019

Event: 22d Microencapsulation Industrial Convention

Date: June 3-6, 2019

Location: Zurich, Switzerland

Information: http://bioencapsulation.net/2019-Zurich-Microencapsulation-Industrial-

Convention/

Event: 26th International Conference on Bioencapsulation

Date: August 27-29, 2019

Location: Strasbourg, France

Information: http://bioencapsulation.net/2019_Strasbourg_International_

Conference_on_Bioencapsulation/

@ Disclaimer: No commercial use of these data is allowed, personal use of TPM-member only. If permission for public use or other use is necessary please contact

the authors of this study via [email protected] or

[email protected].

Upcoming events II.3

http://bioencapsulation.net/2019-Loughborough-Microencapsulation-

http://www.partec.info/en/congress-info/about-2019

http://bioencapsulation.net/2019-Zurich-Microencapsulation-Industrial-

http://bioencapsulation.net/2019_Strasbourg_International_

mailto:[email protected]

mailto:[email protected]

Newsletter III /2018... · Topic: Microencapsulation of reactive components Date: 24th of October...

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