Ver. 1.02008년추계대한화장품학회세미나자료

SU

NJ

IN Since 19

78

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2008.11.8

유기자외선차단제를내포한 Hybrid PMMA 비드

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EU regulation about UVA protection

Additional criteria, minimum of 370nm to ensure broad band protectionCritical Wavelength

Level of UVA protection (measured by in vivo or in vitro methods) at least 1/3 of labelled SPF. (UVA label can be used to highlight achievement of protection level)

UVA Protection

Sun Protection Factor minimum 6. Only 8 defined SPF values allowed

UVB Protection

All products need to comply by 2009, at which point it is expected to be treated as a law.

Products that do not comply with these requirements will not be regarded as ‘Sunscreen Products’

EU Commission Recommendation of 22 September 2006 on the efficacy of sunscreen products and the claims made relating thereto

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UVA Filters

UVA protection with new class of UV absorber, Ciba, Uli Osterwalder14th Congresso nacional de Cosmetologia Sao Paulo, Julion 5-7,2000

Mexoryl SX

Parsol 1789

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BMDBM = Parsol 1789 = Avobenzone

INCI name : Butyl Methoxydibenzoylmethane

BMDBM is the most efficient UVA filter, covering almost the entire UVA range…

The 1st UVA filter approved by FDA in 1988

The most common trade name is Parsol 1789,

but why 1789?

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Solubility of BMDBM

BMDBMDimethicone 0 3

Cyclomethicone 0 50

Mineral oil 1 50

Isostearyl Isosterate 3 50

Octylpalmitate 3 50

Cpric/Caprilic Triglyceride 7 50

Isopropyl Myristate 9 50

PG/Dicaprate/Dicaprylate 5 50

C12-C15 Alkyl Benzoate 11 50

Solubility Data BMDB

M

OMC

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Solubility Test

테스트 문제:

1. BMDBM 1g을 OMC 10g에 완전히 녹인 용액은 안정한 용액 상태일까?

2. OMC 10g을 Cyclomethicone 40g에 완전히 녹인 용액은 안정한 용액 상태일까?

3. BMDBM 1g을 OMC 10g에 완전히 녹인 후 Cyclomethicone 40g에 완전히녹일 수 있을까?

4. 위 용액이 3개월 후에도 안정한 상태로 존재할까?

용해도 자료

BMDBM in OMC = 25%

OMC in Cyclomethicone = 50%

BMDBM in Cyclomethicone = 0%

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Gresham’s law

악화(惡貨)가 양화(良貨)를 구축한다:

Bad Money Drives Out Good

3성분계2성분계

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Shortfalls of BMDBM

The amount of BMDBM decreasesweakening of the UVA protection

(3) Compatibility

(2) Poor Photostablility

Aluminum oxide is one of the most common coating material for TiO2.

BMDBM forms a complex with Al3+ salts from TiO2 coatings

Avobenzone degrades quickly in the sun. Researchers have reported a 36% reduction in UVA absorption by avobenzone after only 15 minutes of exposure. In vitro studies have shown a 50% loss in UVA blockage for different sunscreen formulations, confirming the photodegradation of avobenzone.

(4) Crystallization

BMDBM is susceptible to crystallization that results in loss of product aesthetics, sun protection, appearance, stability

Dimethicone 0 3

Cyclomethicone 0 50

Mineral oil 1 50

Isostearyl Isosterate 3 50

Octylpalmitate 3 50

Cpric/Caprilic Triglyceride 7 50

Isopropyl Myristate 9 50

PG/Dicaprate/Dicaprylate 5 50

C12-C15 Alkyl Benzoate 11 50

Octyldodecanol 13 50

Ethyl Butylacetylaminopropionate

26 50

(1) Poor Solubility BMDB

M

OMC

Bad

Th

ings

1789

?

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Two different Approaches

Surface TreatmentTiO2

TriethoxycaprylylsilaneOptisol AS

Silica, DimethiconeParsol TX

Silica, MethiconeKemira X195

Silica, TriethoxycaprylylsilaneEusolex T-Avo

Silica, TriethoxycaprylylsilaneUV Capsule 60

Protection of TiO2

Encapsulation of BMDBM

Anything New and Better?

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Hybrid PMMA Bead

Easy for Silicone formulation

Water compatible

Good sensorial feeling

Non irritant to the skin / no odor

Improved photo-stability

Physically stable

Long Lasting UV protection like physical filter

2~7BMDBM(Avo Benzone) 25~30%

Octyl Salicylate 5~7%PMMA 62~70%

Hybrid

ABOS

Grade Composition Particle size(um)

Hybrid ABOMC

BMDBM(Avo Benzone) 25~30%

2-Ethylhexyl 4-methoxycinnamate 5~7%PMMA 62~70%

2~7

Chemical UV Filterinside

A Hybrid Car

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Closed Patch Test for Skin Irritancy Test

#1 #2 #3 #4 #5 #6 #7 #8 #9

Distilled Water 10.0 - - - - - - - -

Isohexadecane - 10.0 9.00 9.00 9.00 9.00 9.00 9.00 9.00

SUNPMMA-S - - 1.00 - - - 0.62 0.62 0.62

OMC - - - 1.00 - - 0.38 - 0.31

AvoBenzone - - - - 1.00 - - 0.38 0.07

Hybrid ABOMC - - - - - 1.00 - - -

Irritation Score 0 1 2 5 3 1 3 2 3

#11 #12 #13 #14 #15 #16 #7 #8 #9

Distilled Water 10.0 - - - - - - - -

Alkyl Benzoate - 10.0 9.00 9.00 9.00 9.00 9.00 9.00 9.00

SUNPMMA-S - - 1.00 - - - 0.62 0.62 0.62

OMC - - - 1.00 - - 0.38 - 0.31

AvoBenzone - - - - 1.00 - - 0.38 0.07

Hybrid ABOMC - - - - - 1.00 - - -

Irritation Score 0 0 0 3 0 0 0 3 4

No Skin Irritation

Sample size: 5 subjects(Korean)Study Design: Patch testApplication time: 72hrDosage: 25㎕

Dermal response:0 = No evidence of irritation1 = Minimal erythema, 2 = Readily visible erythema, 3 = Erythema and papules4 = Definite edema5 = Erythema, edema, and papules6 = Vesicular eruption7 = strong reaction spreading

Test Condition:

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500-Da Rule

“The 500-Da rule for skin penetration are: 1)virtually all common contact allergens are under 500-Da, larger molecules are not known as contact sensitizers…they can not penetrate and thus cannot act as allergens in man”

Avobenzone Mw: 310.4OMC Mw: 290Octocrylene Mw: 361

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Photostablility of avobenzone

• Avobenzone alone lost between 56%~70% of the starting material after 30MED

• 126 USA patents were granted between 1984 and 2003 that are concerned with photostabilizing avobenzone

• The task of photostabilizing avobenzone has been a primary focus of sunscreen formulators

• Certain UV filters and chemical additives are known to exert a photostabilizing effect on avobenzone by triplet state quenching

MBC(Methylbenzylidene camphor)

Octocrylene

Diethylhexyl 2,6 naphthalate

Oxybenzone

BEMT

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Photostability test condition

1. Light source: Solar Cell Tester(one port)2. Light intensity: 1000uW/cm2 = 0.001W/cm2

3. Irradiation time: 30min = 30*60sec = 1800sec

4. Light energy = 0.001W/cm2*1800sec = 1.8J/cm2

5. Average 1 MED of Koreans tested = 0.021J/cm2

6. Irradiated MED = 1.8J/cm2 = 85.7 MED0.021J/cm2

Solar Cell Tester

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Photostability Test Results

378 -> 377379 -> 379376379 -> 378378 380Critical Wavelength

16.7 -> 17.118.8 -> 20.227.1 -> 22.617.8 -> 23.317.6 10.6Average UVA PF

4 -> 34 -> 44 -> 45 -> 54 5Boots Star Rating

0.83 -> 0.780.88 -> 0.870.84 -> 0.860.98 -> 0.970.86 0.94UVA/UVB ratio

19.6 -> 23.419.4 -> 20.226.1 -> 25.314.9 -> 18.320.1 10.4SPF (before after 85.7MED)

5050505050Vaseline

33.533.5273030C12-15 Alkyl Benzoate

--101010PMMA-S

---7-Octyl Salicylate

6.56.57-7Octyl Methoxy Cinnamate

--3--Octocrylene

--333BMDBM

10----HYBRID ABOS

-10---HYBRID ABOMC

# 5# 4# 3# 2# 1

Test

Res

ults

Not photostable Photostable

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Theoretical Explanation

== BlockedBlocked

Photodegradation of Avobenzone can be blockedbecause nano sized Avobenzone crystals are immobilized in solid PMMA matrix

OMC/avobenzone combination is well known to be not amenable to photostabilization unless segregated by some means such as encapsulation.

Vs.

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Efficiency comparison between ABOMC and Avobenzone directly inside formula

378 -> 377379 -> 379376379 -> 378378 380Critical Wavelength

16.7 -> 17.118.8 -> 20.227.1 -> 22.617.8 -> 23.317.6 10.6Average UVA PF

4 -> 34 -> 44 -> 45 -> 54 5Boots Star Rating

0.83 -> 0.780.88 -> 0.870.84 -> 0.860.98 -> 0.970.86 0.94UVA/UVB ratio

19.6 -> 23.419.4 -> 20.226.1 -> 25.314.9 -> 18.320.1 10.4SPF (before after 85.7MED)

5050505050Vaseline

33.533.5273030C12-15 Alkyl Benzoate

--101010PMMA-S

---7-Octyl Salicylate

6.56.57-7Octyl Methoxy Cinnamate

--3--Octocrylene

--333BMDBM

10----HYBRID ABOS

-10---HYBRID ABOMC

# 5# 4# 3# 2# 1

Test

Res

ults

The Same Result

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Potential application: Silicone Gel Based Formulas

Cream Foundation

Primer

Skin Care

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Potential applications

Consumer Needs

Formulation

UVA Protection

Good Sensory

Minimum irritancy

Silicone Gel Based Formula

Silicone Formula(W/Si)

Water Formula

Wax Base Formula

High Transparency

Powdery, Pressed make-up

Skin care

Sun care

Make-up

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Summary

Korean Patent appliedNo. 10-2007-0083469

US Patent Application No. 11/872,456“POLYMER COMPOSITE PARTICLES CONTAINING SUNSCREEN AGENT AND MANUFACTURING METHOD THEREOF”

Japanese Patent Application 特願 2007-272539

Chinese Patent Application

Globally patented

Only One or Number One