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Silicone Alternatives & Formulation Technologies
2019.5.24
SUNJIN BEAUTY SCIENCE
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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
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1. What is Silicone?
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Silica to Silicon
Si: SiliconSiO2: Silica
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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
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Silicon to Silicone
Silicone
Chlorosilane
Silicon
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Sand to Silicone
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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
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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
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Silicone Polymers
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Most common INCI names for silicone
INCI dictionary documents more than 500 silicone materials derivatives
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Silicone in Personal Care
Silicones for Personal Care, 2nd Edition, p8Anthony J. O’Lenick Jr.
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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
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2. Regulations about Silicone
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18https://www.compass.or.kr/news.do?command=view&selected_key=01880
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한국소비자원, 업계에 환경 생태계 오염 생물체 잔류 유발 성분사용 제한 요청2018.12.21
일요경제(http://www.ilyoeconomy.com)
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D5 ban will be extended to leave on
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SCCS vs. ECHA
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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
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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
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The environment is a luxury goodTim Worstall, Adam Smith Institute
The Signaling Theory of Marketing
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3. Clean Beauty
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https://www.skinstore.com/natural/silicone.list?pageNumber=2
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https://shop.nordstrom.com/c/beauty-skincare-all-skincare/silicone-free-products
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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
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Clean Cosmetics
Paraben-freePhtalate-freeFormaldehyde-freeChemical sun screen-freeTriclosan-freePEG-freeSulfate-freePetrolatum-freePhenoxyethanol-freeMicrobead-freeCruelty-free
https://www.skinstore.com/natural/silicone.list?pageNumber=2
35https://cleanbeautybox.com/pages/definition-of-clean-beauty
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"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
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4. Silicone Alternatives
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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
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Silane Methane
Silane is analogous to Alkane
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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
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Silicone Resin Powder
Si O SiOO
SiSi
R R
O O
O
RR
OSi O
OOSi
R
OR
R = Methyl
Polymethylsilsesquioxane
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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
56Copyright © 2019 by SUNJIN BEAUTY SCIENCE ALL RIGHTS RESERVED.
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
57Copyright © 2019 by SUNJIN BEAUTY SCIENCE ALL RIGHTS RESERVED.
Hectorite
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Alkyl Silane
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Alkyl Silane Coating Alternative
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5. Silicone Free Skin CareCase Study
61Copyright © 2019 by SUNJIN BEAUTY SCIENCE ALL RIGHTS RESERVED.
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
62Copyright © 2019 by SUNJIN BEAUTY SCIENCE ALL RIGHTS RESERVED.
Water Drop Hydro-gel
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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”?
64Copyright © 2019 by SUNJIN BEAUTY SCIENCE ALL RIGHTS RESERVED.
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
65Copyright © 2019 by SUNJIN BEAUTY SCIENCE ALL RIGHTS RESERVED.
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
66Copyright © 2019 by SUNJIN BEAUTY SCIENCE ALL RIGHTS RESERVED.
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
67Copyright © 2019 by SUNJIN BEAUTY SCIENCE ALL RIGHTS RESERVED.
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
68Copyright © 2019 by SUNJIN BEAUTY SCIENCE ALL RIGHTS RESERVED.
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
69Copyright © 2019 by SUNJIN BEAUTY SCIENCE ALL RIGHTS RESERVED.
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
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Have you heard of “Silicone Free Water Drop” system?
Not really, right?
Then Let’s study some market Water Drop Products by Silicone system
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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
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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.
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Key factors to make water drop system
1. Inner(Water) Phase %
2. Oil Phase polarity:
3. Emulsion Droplet Size
- Emulsifier %
- Shear Force(RPM)
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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
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Emulsion Size
Semi Water DropMacro Emulsion
Water Drop Macro Emulsion
RegularMacro Emulsion
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How to stabilize Big Emulsion Droplet?
1. Silicone Oil
2. Silicone Emulsifier
3. Silicone Gel
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Crosslinked Silicone Polymer
W/S Water Drop System 모식도
Silicone EmulsifierSilicone Oil
79Copyright © 2019 by SUNJIN BEAUTY SCIENCE ALL RIGHTS RESERVED.
Droplet under Microscope
Silicone Free Water DropW/S Water Drop