silicone alternatives & formulation...

1

Silicone Alternatives & Formulation Technologies

2019.5.24

SUNJIN BEAUTY SCIENCE

2

Topics

1. What is Silicone?2. Regulations about Silicone3. Clean Beauty4. Silicone Alternatives

• Silicone Oil• Silicone Emulsifier• Silicone Gel• Silicone Coating

5. Silicone Free Skin Care, Case Study

3

1. What is Silicone?

4

Silica to Silicon

Si: SiliconSiO2: Silica

5

Silicon

Si14

28.0855

1410

2355

1.11

1.8

원자번호

원자량

녹는점(oC)

끓는점(oC)

공유반경(10-10 m)

전기음성도

주기율표상 14번 원소(탄소와 같은 4족 원소)Berzelius에 의하여 최초로 원소로서 분리 - 1823지각의 구성물질 중 산소 다음으로 풍부한 약 28 % 가 Silicon탄소-규소의 결합은 자연발생적으로는 일어나지 않음

6

Silicon to Silicone

Silicone

Chlorosilane

Silicon

7

Sand to Silicone

8

Methyl기 간의 작은 상호작용

Si

CH3

CH3

CH3

O

CH3

SiOO

Si

CH3

CH3

O

CH3

Si

OO

CH3

발수효과 / 친유성 + 통기성

Low level of activity /Biocompatibility

- Low surface tension

- Low Tg ( Dimethicone : - 127도)

- 높은 퍼짐성

강한 공유 결합 / Ozone, UV, 고열에 강함

Flexible chain / 온도에 따른 물리적

특성 변화가 작음

Characteristics of Silicone

9

Characteristics of Silicone

• Wide range of thermal stability(high and low temp)

• Resistance to oxidation, ozone, UV exposure• Low surface tension(good wetting, spreading flow

and antifoaming)• Good dielectric properties• Water repellency• Low flammability• High gas permeability• High compressibility and shear resistance• Adhesive or dehesive properties• Softeness/flexibility

10

Silicone Polymers

11

Most common INCI names for silicone

INCI dictionary documents more than 500 silicone materials derivatives

12

Silicone in Personal Care

Silicones for Personal Care, 2nd Edition, p8Anthony J. O’Lenick Jr.

13

History of Silicones in Skin Care

• In 1953, Revlon commercialized a hand cream called Silicare, “Silicare forms an invisible glove to protect your hands”

• In the 1960s, the use of volatile silicone dramatically improved the overall quality of antiperspirant products

• From the 1980s, the use if silicone materials expanded to all skin care segments and was recognized as a turning point, an entirely different feel and solubility characteristics, offering new possibilities versus conventional organic materials

• In the mid 1990s, silicone resins combined with volatile silicones were introduced in makeup formulations claiming to last all day. Volatile silicones evaporate, leaving the pure pigments held in place by a film of silicone resin, resulting in color adhesion to lips for 8 to 10 hours. Revlon demonstrated the transfer resistance of its Ultima II formulation using a “Kiss Test.” Panelists were instructed to apply the lipstick, wait 5 minutes and then kiss the back of their hand, with the result that most of them reported hardly a trace of color

• At the turn of the 21st century, the introduction of silicone elastomers offered unique replacements and modification of properties for traditional high oil and fatty alcohols systems. These high molecular weight cross-linked silicones brought alternative texture and feel dimensions to skin care and color cosmetic products. Elastomer powders also provide distinctive aesthetic properties that can range from smooth and silky to powdery with a dry soft finish. In particular, they were key materials in a new type of application, so called “skin primer”

• Silicones have been used in skin care products for more than 50 years and still maintain a very high use level today. Silicones are present in more than 50% of new launched skin care products in 2015

16

2. Regulations about Silicone

18https://www.compass.or.kr/news.do?command=view&selected_key=01880

https://www.compass.or.kr/news.do?command=view&selected_key=01880

19

한국소비자원, 업계에 환경 생태계 오염 생물체 잔류 유발 성분사용 제한 요청2018.12.21

일요경제(http://www.ilyoeconomy.com)

http://www.ilyoeconomy.com/news/articleView.html?idxno=41070

20

D5 ban will be extended to leave on

22

SCCS vs. ECHA

24

Science Based vs. Precautionary

Science-based regulation expressed the belief that regulation should be

based on the best available quantitative scientific evidence. This type of regulation considers actual harm to human health or the environment, not just the potential for harm

By contrast, the precautionary principle expresses the belief that “when an

activity raises threats of harm to human health or the environment, precautionary measures should be taken even if some cause-and-effect relationship are not fully established

Regulators have long been concerned about silicones, because of their potential impact on human health. In this paper, we will compare the science-based regulatory approach of the Canadian and

Australian governments with the regulatory approach of the European Chemicals Agency(ECHA), which is informed by the precautionary principle

In recent years, regulation have rightfully looked at the potential health and environmental risks posed by D4, D5, and D6. One important issue was the direct impact on human health, including reproductive risk. Another issue was the potential for these chemicals to accumulate in the environment rather than break down, including accumulating in marine life

25

Silicone Regulation in EU

The European approach to silicone regulation in particular, and chemicals regulations in

general, relies much more heavily on the precautionary principle

The Regulation is based on the principle that it is for manufacturers, importers and downstream users to ensure that they manufacture, place on the market or use such substances that do not adversely affect human health or the environment. Its provisions are underpinned by the precautionary principle

Unlike in Canada, the EU law does not require regulators to examine real-world data about how these materials behave in the environment

The basis of both regulation in these materials exhibit hazardous properties according to certain lab results.

D4, D5, D6 were identified by ECHA’s member as SVHC(Substances of Very High Concern) with PBT(Persistent, bioaccumulative and toxic) / vPvB(very Persistent and very

Bioaccumulative) properties. PBT/vPvB substances give rise to specific concerns based on their properties to accumulate in the environment and cause effects that are unpredictable in the long-term and are difficult to reverse even when releases cease

An SVHC designation effectively creates a “blacklist” and could be viewed as an initial step

to regulating a substance at a global level through the Stockholm Convention

26

The environment is a luxury goodTim Worstall, Adam Smith Institute

The Signaling Theory of Marketing

27

3. Clean Beauty

29

https://www.skinstore.com/natural/silicone.list?pageNumber=2


30

https://shop.nordstrom.com/c/beauty-skincare-all-skincare/silicone-free-products

https://shop.nordstrom.com/c/beauty-skincare-all-skincare/silicone-free-products

31

It might seem like a simple question: Why do people buy natural products?According to a report from Denise Herich of The Benchmarking Company, 68% of consumers buy natural and organic products. Of those surveyed, 95% said they buy more natural products than they did 10 years ago.

At the same time, 95% of consumers surveyed cite product efficacy as the most important factor when they choose products. As a result, the cosmetic market is evolving to support priorities like safety, performance and responsibility.

https://www.gcimagazine.com/marketstrends/segments/skincare/Silicones-Rethinking-Clean--Safe-Beauty-504320161.html

https://www.gcimagazine.com/marketstrends/segments/skincare/Silicones-Rethinking-Clean--Safe-Beauty-504320161.html

34

Clean Cosmetics

Paraben-freePhtalate-freeFormaldehyde-freeChemical sun screen-freeTriclosan-freePEG-freeSulfate-freePetrolatum-freePhenoxyethanol-freeMicrobead-freeCruelty-free



35https://cleanbeautybox.com/pages/definition-of-clean-beauty

39

"Sephora continues to demystify beauty choices for clients, helping them find the right products

for them, based on their lifestyle needs," says Artemis Patrick, chief merchandising officer for

Sephora. "Many of them are looking to shop brands and products that are 'free of' and Sephora

is responding to help them do that, easily and conveniently in-store, online, and on mobile." It's

that philosophy of "free of" — meaning free of certain questionable and unwanted ingredients

far beyond parabens, sulfates, and phthalates — that guides this new initiative, which starts

June 1. "Together with Sephora’s brands, industry experts, external council — including

feedback from clients — Sephora has curated a partnership with its brands across cosmetics,

skin care, hair care, and fragrance that stand behind the 'Clean at Sephora' category.“

And they're not starting small. Fifty brands are already

signed on, and each one will feature a "Clean at Sephora"

seal, and more than 2,000 product pages

on sephora.com will be clearly marked as "clean." The

category will even have its own landing page online and in-

store area in shops nationwide. Online buying guides and

education sections, Beauty Insider Community

conversations, and Sephora app features will help shoppers

gain a better understanding of the category's standards and

how they apply to their lifestyle and beauty routine

https://www.sephora.com/

https://www.sephora.com/community

46

4. Silicone Alternatives

47

Cyclomethicone Alternatives

Aprinnova, HemisqualaneIMCD, Smart5(synthetic hydrocarbon)Seppic, EmogreenBiosynthis VegelightBASF, Cetiol CC, C5CThe Innovation Company, DedraflowDr Straetmans, Dermofeel MCTGova, GosulinAlban Muller, LipolamiDubois, Dub ZenoatGreentech, Softbutter

48

Silane Methane

Silane is analogous to Alkane

52

KF 6038: Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone

KF 6028:PEG-9 Polydimethylsiloxyethyl Dimethicone

KF 6017:PEG-10 Dimethicone

Silicone Emulsifiers Comb-like

53Copyright © 2019 by SUNJIN BEAUTY SCIENCE ALL RIGHTS RESERVED.

Silicone Emulsifier Alternatives

DEHYMULS PGPH :Polyglyceryl-2 DipolyhydroxystearateBASF

Isolan GI 34 : Polyglyceryl-4 IsostearateEVONIK

Radia 7887 : Polyglyceryl-4 Isostearate &Sorbitan isostearateOLEON

54

Silicone Resin Powder

Si O SiOO

SiSi

R R

O O

O

RR

OSi O

OOSi

R

OR

R = Methyl

Polymethylsilsesquioxane

55

Swollen Gel

Addition Reaction

Pt,

Milling

Blending

CH3 SiO

CH3

CH3

SiO

CH3

CH3

SiO

R1

R2

Si

CH3

CH3

CH3

m n

C

H

H

CH

C

H

H

C

H

H

CH

C

H

H

XSiO

CH3

CH3

CH3

CH3

SiO

Silicone Gel


Self-Assembly Oleogel

Crystal ParticleSuspension Oleogel

Fatty Acids

Hydroxy Fatty Acids

Fatty Alcohols

Wax Esters

High-melting Triacylglycerols

Carnauba Wax

Rice bran Wax

OLEOGEL

Surface modified Bentonite or Hectorite

Ceramide

Lecithin

Sorbitan Stearate

Monoacylglycerol

Modified Silicone Polymer

Fumed Silica

Organo Clay:

Silicone Gel Alternatives


Hectorite

58

Alkyl Silane

59

Alkyl Silane Coating Alternative

60

5. Silicone Free Skin CareCase Study


INGREDIENTS: PR-016935 Aqua, Dimethicone, Glycerin,

Dimethicone/Vinyl Dimethicone Crosspolymer,

Sodium Hyaluronate, Ethylhexylglycerin, Dimethiconol,

Cetearyl Olivate, Sorbitan Olivate, Laureth-7, C12-14 Pareth-

12, Polyacrylamide, Dimethicone Crosspolymer, Carbomer,

C13-14 Isoparaffin, Sodium Hydroxide, Phenoxyethanol,

Chlorphenesin, Methylparaben, Benzoic Acid, Parfum, CI

42090.

NeutrogenaHydro Boost Water Gel


Water Drop Hydro-gel

63

Water Drop = Water-releasing = Quick Breaking

Shearing forces generated by the rubbing in or

application of the cosmetic composition cause the water-in-oil type emulsion to rupture, thereby causing the internal aqueous phase to emerge in the form of droplets

Macro emulsion by Minimized use of emulsifier and

increased inner phase % causes Water Drop Effect

What is “Water Drop”?


INGREDIENTS: Aqua, Glycerin, Dimethicone,

Propanediol, Dimethicone/PEG-10/15 Crosspolymer,

Phenoxyethanol, Sodium Chloride, Polymethylsilsesquioxane,

Chlorphenesin, Citric Acid, Sodium Citrate, Limonene, PEG-

10 Dimethicone, Disodium EDTA, Butylene Glycol, Sodium

Hydroxide, Vitreoscilla Ferment, Tocopherol, Glycine Soja Oil,

Adenosine, Dipropylene Glycol, Benzyl Salicylate, Linalool,

Benzyl Alcohol, Citral, Alteromonas Ferment Extract Geraniol,

Parfum, [+/- CI14700]

BiothermAQUASOURCE EVERPLUMP


INGREDIENTS:

Aqua, Glycerin, Dimethicone, Propanediol,

Hydroxyethylpiperazine Ethane Sulfonic Acid,

Dimethicone/PEG10/15 Crosspolymer, Nylon-12,

Pentylene Glycol, Polymethysilsesquioxane, Phenoxyethanol,

Sodium chloride, Chlorphenesin, Silica Silylate, butylene Glycol,

Sodium Citrate, p-Anisic Acid, Biosaccharide Gum-1,

Carrageenan, Disodium EDTA, PEG-10 Dimethicone, Sodium

Hydroxide, Adenosine, Hydrolyzed Opuntia Ficus-Indica Flower

Extract, Synthetic Fluorphlogopite, Titanium Dioxide, Poterium

Officinale Root Extract, Zingiber Officinale (Ginger) Root Extract,

Cinnamomum Cassia Bark Extract, Ethylhexylglycerin, Benzyl

Alcohol, Iron Oxide Red, Ponceau SX, CI 19140, Tin Oxide,

Fragrance

YvesSaint LaurentTop Secret instant moisture glow


INGREDIENTS:

Aqua, Glycerin, Dimethicone, Propanediol,

Dimethicone/PEG10/15 Crosspolymer,

Polymethysilsesquioxane, Sodium chloride, Phenoxyethanol,

Chlorphenesin, Sodium Citrate, p-Anisic Acid, Disodium

EDTA, PEG-10 Dimethicone, Sodium Hydroxide,

Adenosine, Dipropylene Glycol, Limonene, Butylene Glycol,

Butylphenyl Methylpropional, Tocopherol, Citrus Junos Fruit

Extract, Citric Acid, Parfum

Shu Uemuramaxi. Hydrability essence in gel


INGREDIENTS: Goat milk, Glycerin, Cyclopentasiloxane,

Propanediol, Niacinamide, Dimethicone, Dimethicone/PEG-10/15

Crosspolymer, Sodium chloride, Piper methysticum leaf/root/stem

extract, Phellinus linteus extract, Arctium lappa root extract, Portulaca

oleracea extract, Pueraria thunbergiana root extract, Glycyrrhiza glabra

root extract, Paeonia Albiflora Root Extract, Paeonia Lactiflora Root

Extract, Cnidium Officinale Root Extract, Cnidium Officinale Rhizome

Extract, Soluble collagen, Aloe Barbadensis Leaf Juice, Hydrogenated

lecithin, Sodium Hyaluronate, Titanium Dioxide, Sodium Citrate,

Mannitol, Ethylhexylglycerin, PEG-10 Dimethicone, PEG-9

Polydimethylsiloxyethyl Dimethicone, Mica, Water, Adenosine,

Butylene glycol, PEG-12, Ethylcellulose, Hydroxypropyl methylcellulose,

Xanthan Gum, Hydrolyzed Hyaluronic Acid, Panthenol, Provitamin B5,

Folic Acid, Ceramide NP, Ceramide 3, Cholesterol, Raffinose,

Tromethamine, Palmitoyl Pentapeptide-4, Palmitoyl Pentapeptide-3,

Fragrance, Phenoxyethanol, Red Iron oxide, Yellow Iron oxide

TONYMOLYGoat milk Premium Cream


INGREDIENTS :

Water, Dimethicone, Cyclopentasiloxane, Butylene Glycol, Arbutin,

Dimethicone/PEG-10/15 Crosspolymer, Ulmus Davidiana Root

Extract, Amaranthus Caudatus Seed Extract, Piper Methysticum

Leaf/Root/Stem Extract, Glycyrrhiza Glabra (Licorice) Root Extract,

Portulaca Oleracea Extract, Paeonia Lactiflora Root Extract, Cnidium

Officinale Root Extract, Pueraria Thunbergiana Root Extract, Citrus

Aurantium Bergamia (Bergamot) Fruit Oil, Soluble Collagen, Aloe

Barbadensis Leaf Juice, Citrus Aurantium Dulcis (Orange) Oil, Citrus

Medica Limonum (Lemon) Fruit Oil, Cymbopogon Schoenanthus Oil,

Hydrogenated Lecithin, Cymbopogon Nardus (Citronella) Oil, Geranium

Maculatum Oil, Sodium Hyaluronate, Argania Spinosa Kernel Oil,

Panthenol, Niacinamide, Sodium Chloride, Tocopheryl Acetate,

PEG/PPG-19/19 Dimethicone, Adenosine, Sodium Metabisulfite,

Xanthan Gum, Glycerin, Biotin, Ascorbyl Glucoside, Bisabolol, Retinol,

Tocopheryl Linoleate, Squalane, Dicaprylyl Carbonate, Ceramide 3,

Sucrose Distearate, Folic Acid, Raffinose, Alcohol, Cholesterol, BHT,

Tromethamine, Palmitoyl Pentapeptide-4, Phenoxyethanol,

Methylisothiazolinone

Dr. JartV7 Relief Vita Drop


INGREDIENTS :

Water, Cyclopentasiloxane, Glycerin, Cyclohexasiloxane,

Niacinamide, 1,2-Hexanediol, Sodium chloride, Cetyl PEG/PPG-10/1

Dimethicone, Phenoxyethanol, Silica, Dimethicone/PEG-10/15

Crosspolymer, Sodium citrate, Citrus limon(lemon) peel oil, Citrus

aurantium bergamia(bergamot) fruit oil, Santalum album(sandalwood)

oil, Dimethicone crosspolymer, Dipotassium glycyrrhizate, Disodium

EDTA, Raffinose, Centella asiatica extract, Camellia sinensis leaf water,

Hippophae rhamnoides fruit extract, Sodium PCA, Hydrolyzed viola

tricolor extract, Butylene glycol, Ethyl hexanediol, Sodium hyaluronate,

Caprylyl glycol, Ethylhexylglycerin

Dr. JartWhitening Water Drop

https://www.google.com/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&ved=2ahUKEwiI84qPotHeAhVK6bwKHf2FBGUQjRx6BAgBEAU&url=https://www.stayfavful.com/products/dr-jart-water-drop-hydrating-moisturizer&psig=AOvVaw3cePLzhq-rjNI0bqBmIBVc&ust=1542194953898023

70

Have you heard of “Silicone Free Water Drop” system?

Not really, right?

Then Let’s study some market Water Drop Products by Silicone system

71

iRecipe Berry Balm 2019

INGREDIENTS :

Water, Caprylic/capric triglyceride ,Glycerin, Ozokerite,

Dicaprylyl Carbonate, Polyglyceryl-4 Isostearate, Propanediol,

Stearyl Heptanoate, 1,2-Hexanediol, Disteardimonium Hectorite,

Ceramide, Sodium Chloride, Stearyl Caprylate, Butylene Glycol,

Tocopherol, Fragrance, Rubus Fruticosus(Blackberry)

Fruit Extract, Ribes Nigrum(Black Currant) Fuit

Extract, Vaccinium Angustifolium(Blueberry) Fruit Extract,

Euterpe Oleracea Fruit Extract, CI 17200

73

Hello, hydrated skin. Quenching and cooling upon application, our gentle, advanced moisture-release cream delivers firmer, smoother, more supple-feeling skin — all while helping to reduce the appearance of fine lines and imparting an instant dewy glow

MADE WITHOUT: Parabens, Silicones, Petrolatum, Mineral Oil, Synthetic Fragrances, Dyes

INGREDIENTS:Water (Aqua), Squalane, Glycerin, Polyglyceryl-4 Isostearate, Pyrus Malus (Apple) Fruit Extract, Coco-Caprylate/Caprate, Propanediol, Disteardimonium Hectorite, Jojoba Esters, Sodium PCA, Tocopherol, Sodium Acetylated Hyaluronate, Hydrolyzed Sodium Hyaluronate, Trisodium Ethylenediamine Disuccinate, 1,2-Hexanediol, Caprylhydroxamic Acid.

74

Key factors to make water drop system

1. Inner(Water) Phase %

2. Oil Phase polarity:

3. Emulsion Droplet Size

- Emulsifier %

- Shear Force(RPM)

75

10nm 100nm 1µm 100µm

Clear to translucentBluish

iridescenceVisible droplets

MicellarSolution

Nano or Micro

Emulsion

Mini Emulsion

Macro Emulsion

Opaque & White

Bi-LiquidSystem

Blue NanoEmulsion

Semi Water DropMacro Emulsion

Water Drop Macro Emulsion

Regular Emulsion

50nm 0.5umEmulsion Droplet Size

76

Emulsion Size

Semi Water DropMacro Emulsion

Water Drop Macro Emulsion

RegularMacro Emulsion

77

How to stabilize Big Emulsion Droplet?

1. Silicone Oil

2. Silicone Emulsifier

3. Silicone Gel

78

Crosslinked Silicone Polymer

W/S Water Drop System 모식도

Silicone EmulsifierSilicone Oil


Droplet under Microscope

Silicone Free Water DropW/S Water Drop

silicone alternatives & formulation...

Documents