hdrs – colipa-tf sun protection 1994 / venice hdrs – the future of spf · 2019. 12. 29. ·...

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HDRSHybrid Diffuse Reflectance Spectroscopy

The first real change in SPF-testing since COLIPA 1994

Mathias Rohr

www.schrader-institute.de

HDRS – COLIPA-TF Sun Protection 1994 / Venice

Published May 1994


HDRS – The Future of SPF

Albert Einstein (1879-1955)

Die Probleme dieser Welt lassen sich nicht mit den gleichen Denkweisen lösen, die sie erzeugt haben!

A whole new way of thinking is required forsolving the problems we have created through our old way of thinking!

Let’s Start and

Let’s talk about Hybrid Diffuse Reflectance Spectroscopy or ISO 23698


ISO 24444 – SPF Measurement

Application

Test ProductIrradiation

of Test Product

SPFof

Test Product

Expected SPF Range

Volunteer recruitment

Definition of spectrum

Range finding

Definition of MED

Reading of MED

Waiting Time 16-24h

Energy - Homogeneity

Certificates


ISO 24444 – UVB Erythema / MED

UVB-Erythema

156%

125%

MED = 100%

80%

64%

51%

MED


ISO 24444 – UVB Erythema?

UVB-Erythema?

Beside any Ethical Concernssometimes even the simple definition of

the correct MED might be a challenge

In order to get rid of all these points

Future SPF-Testing should be „free off“

any Erythemal Testing


Basic Ideas of HDRS

Basic Ideas of HDRS

Technique

Results / SPF / Photostability

Results / UVA-PF

Results / Water-Resistance

Ongoing Statistics - ISO

Summary


SPFHDRS – A combination of in vivo and in vitro calculations

SPFcalculated =

E( ) I( ) 10 –A( ) d=290

=400

E( ) I( ) d=290

=400

E( ) = Erythemal Action SpectrumI( ) = Spectral IrradianceA( ) = Absorbance

SPF-Calculation

Experimental Design HDRS: Combination of ISO 24443 (in vitro) and Diffuse Reflectance Spectroscopy (DRS in vivo)


300 320 340 360 380 4000.0

0.5

1.0

1.5

2.0

2.5 DRS in vivo (Skin)

Wavelength [nm]

Abso

rptio

n [O

D]

HDRS – DRS-Signal

No Signal


300 320 340 360 380 4000.0

0.5

1.0

1.5

2.0

2.5 DRS in vivo (Skin)

Wavelength [nm]

Abso

rptio

n [O

D]

SPFHDRS – Hybrid-Signals

HDRS-Signal

300 320 340 360 380 4000.0

0.5

1.0

1.5

2.0

2.5 DRS in vivo (Skin) UV in vitro (PMMA)

Wavelength [nm]

Abso

rptio

n [O

D]

AdjustmentHybridisation Wavelength


SPFHDRS – A combination of in vivo and in vitro calculations

SPFcalculated =

E( ) I( ) 10 –A( ) d=290

=400

E( ) I( ) d=290

=400

E( ) = Erythemal Action SpectrumI( ) = Spectral IrradianceA( ) = Absorbance

SPF-Calculation HDRS

SPF-Calculation based on A( ) from HDRS-Data


Technique

Basic Ideas of HDRS

Technique


Results / UVA-PF



Summary


SPFHDRS – Technique

Light

Sou

rce

Diffuse Reflectance DRS / in vivo

Signal analysis

Excitationmonochromator

Emissionmonochromator

UVB / UVADetection

Hardware configuration

ISO 24443UVB / in vitro

Ligh

LighghghhhhghghgLiLiLLLLLLLLL

SoSoSoSot So

tSo

tSoSotSoSot SoSotSo

tSo

t SoSoootSooooSoooSoSoSoooooSooSooSot SooSSSSSSSSSSStSSSSSSSSt SSSSSSSSS

urce

urc

urccrcccrcurcc

urccccccccccc

urccc

urcccrcrcccurc

urc

urc

urcc

urc

urcc

urccrrrrruuuuuuuuuuuuu

Diffuse ReflectannnccccccccceDRS / / in vivo

ExExcitExExExcitExcitExcitExcittEExcitEE ititatatioatatioationationttiontiontitionoonationatiattitittiotionataati nnatiaatttiottttiioonooooonnnnnatationatioonnamonocmonocmonocmonocmonomonooonnnmonononmononomonoonomonomonocmonoccmonocmonocnocmonocmonooonocmonomomooonoo oonoocccccmonommono ooomonomonocmonococmonocmonmmmmmm nnnomonocmmmmmonocmmmmoooommmmmmmm nmm hhhhhhhhhhhromhromromromromahromahromahromahromromhromhromhhhhhromhromhhhhhhrohrohrohrhrhroohrhrohrh torrrorrrrrrrrrorrrrrroorrrrrrooorrrrr

g

ISOISOISOISOISISOSOISOISSOISOSOSOOOISOISOISOSSOIIISSSSISOSISISSSSSSOSOSSSOSSSSOOSOOISOISOSSOSOSOSOOOOSOOSOOSOISOOISOSOSSSOOOOOOOOOOISSOSOOOOIS 242424242422242424422224244222222222244444242242244444444443443433333333443333333333333443443444333334444444 33UVBUVBUVUVBUVBUUVBUVBUVBBUVBUUVUUUUUVBUVUUUUUUUUUUUUUUUUVBUVBUVBVBUUUUUUUUUUVBVVVBUUUUUUUUUVBVBUUUUUUVBUVBVVUVBUUUUUVVUUUUUVVBUUUUUUVB // / / //////// inin iniiniininnnnin vvvvvvvviiiiiittvvvvivviivivvvvvvvvvvvvvviiiv


SPFHDRS – Technique

Bentham 2 Monochromator System

Bi-Alkali PMT - cooled

Measurement range 200 – 650 nm

450 Xenon Lamp

Y-Quartz-Fiber with optically separated excitation and detectionfixed on a specially designed stand

Dynamic Range up to 6 OD

Bentham 2 Monochromator Sysssssssttt

Bi-Alkali PMT - cooleedddddddd

Measurement range 200 – 650 nm

450 Xenon Lamp

Y-Quartz-Fiber with oppppppppseparated excitation aaaannnnfixed on a specially deeessssss

Dynamic Range up to 666

tittitiititiittitiittiiit tttuteuteuteuteute dddddedededede

TeTeTeTeechchchchc ninininiquququququqqq eeeee



Basic Ideas of HDRS

Technique


Results / UVA-PF



Summary


HDRS – Test-Design

Study Objective: Quantification of SPF

Experimental Design: Combination of ISO 24443 (in vitro) and Diffuse Reflectance Spectroscopy (DRS in vivo)

Test Products : 250 Products (marked and specially designed)

SPF-Range : SPF 4 - SPF 120

Subjects: SPF24444 (n=10) / SPFHDRS (n=10-15)

Statistical Analysis: SPF24444 and SPFHDRS / Regression Analysis…….

ISO 24444 (SPF in vivo)


HDRS – Test-Products

Test Products: O/W-Lotion and CreamW/O-Lotion and CreamCream GelO/W-SprayOil-Spray (with and without Alcohol)StickAerosol-SprayPowderFoam

UV-Filter: A wide range of organic and inorganic UV-FilterWith and without TiO2 (Nano and Non-Nano)With and without ZnO

Photostability: Photo-stablePhoto-unstable (UVB and/or UVA)


HDRS – Results SPF24444 / SPFHDRS / n=250

0 20 40 60 80 100 1200

20

40

60

80

100

120

SPF

[HDR

S]

SPF [ISO 24444]

n=250

Linear Fit: m = 0.983 / R2 = 0.974

SPFHDRS approved


SPFHDRS – approved

Photo-Stability adjusted

No limits concerning the type of formulation

Excellent Correlation of SPF24444 and SPFHDRS up to SPF 120


0 20 40 60 80 100 1200

100

200

300

400

SPF

[HDR

S] [N

ot a

djus

ted]

SPF [ISO 24444]

n=250

0 20 40 60 80 100 1200

100

200

300

400

SPF

[HDR

S] [N

ot a

djus

ted]

SPF [ISO 24444]

n=250


Expected Correlation

Calculated

How to include Photo-Stability?


HDRS – Photo-Stability / Limits of pre-Irradiation Dose

Using ISO 24443

How to include Photo-Stability

Pre-Irradiation Dose according to ISO 24443 (1.2 x UVA-PF0 [J/cm2])


280 300 320 340 360 380 4000.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

in vitro UV-Absorption - Before pre-irradiation in vitro UV-Absorption - After pre-irradiation

Wavelength [nm]

Abso

rptio

n [O

D]

280 300 320 340 360 380 4000.00.20.40.60.81.01.21.41.61.82.02.2


Wavelength [nm]

Abso

rptio

n [O

D]

280 300 320 340 360 380 4000.00.20.40.60.81.01.21.41.61.82.02.2


Wavelength [nm]

Abso

rptio

n [O

D]

Absorption – Variation of UV-Stability (PMMA)

Stable UVA-Unstable

UVB-Unstable

SPFcalculated =

E( ) I( ) 10 –A( ) d=290

=400

E( ) I( ) d=290

=400


280 300 320 340 360 380 4000.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8


Wavelength [nm]

Abso

rptio

n [O

D]

280 300 320 340 360 380 400

0

5

10

15

20

25

30

35

Before pre-irradiation After pre-irradiation

Wavelength [nm]

10Ab

sorp

tion

[OD]

280 300 320 340 360 380 4000.00.20.40.60.81.01.21.41.61.82.02.2


Wavelength [nm]

Abso

rptio

n [O

D]

280 300 320 340 360 380 4000

10

20

30

40

50

60

70

80

Before pre-irradiation After pre-irradiation

Wavelength [nm]

10Ab

sorp

tion

[OD]

SRPD – Spectral Ratio of Photo Degradation

UVA-UnstableUVB-Unstable

= 1111 10 ( )10 ( )Photostability: Multiplication of AHDRS with the defined SRPD wavelength by wavelength

Calculation of SPFHDRS300 320 340 360 380 4000.5

0.6

0.7

0.8

0.9

1.0

1.1

mainly UVB mainly UVA

Wavelength [nm]

SRPD

[a.u.

]

SRPD

Ratio of Absorption Curves



No PhotostabilityPhotostabilityadjusted

0 20 40 60 80 100 1200

100

200

300

400

SPF

[HDR

S] [N

ot a

djus

ted]

SPF [ISO 24444]

n=250

0 20 40 60 80 100 1200

20

40

60

80

100

120

SPF

[HDR

S]

SPF [ISO 24444]

n=250

Linear Fit: m = 0.983 / R2 = 0.974



Using ISO 24443



Is there a reason to define a maximum pre-Irradiation Dose?


0 2 4 6 8 10 12 14 160

1000

2000

3000

4000

5000

6000

7000

8000

Dose

per

Day

[J/m

2 d]

UV-Index

HDRS – Limits of pre-Irradiation Dose

0 2 4 6 8 10 12 14 160

1000

2000

3000

4000

5000

6000

7000

8000 Dose per Day

Dose

per

Day

[J/m

2 d]

UV-Index

0 2 4 6 8 10 12 14 160

1000

2000

3000

4000

5000

6000

7000

8000 Dose per Day Linear Fit : m = 522.0 / b = -106.4 / R2 = 0.993

Dose

per

Day

[J/m

2 d]

UV-Index

0 2 4 6 8 10 12 14 160

5

10

15

20

25

30 SED Skin Type II (250 J/m2)

Linear Fit : m = 2.09 / b = -0.43 / R2 = 0.993

MED

per

Day

[250

J/m

2 d]

UV-Index(Data from: Knuscke et. all, Bundesamt für Arbeitsschutz und Arbeitsmedizin, Schutzkomponenten bei solarer UV-Exposition – Forschungr Projekt F2036, 2015)


HDRS – Limits of pre-Irradiation Dose

0 2 4 6 8 10 12 14 160

5

10

15

20

25

30 SED Skin Type II (250 J/m2)

Linear Fit : m = 2.09 / b = -0.43 / R2 = 0.993

MED

per

Day

[250

J/m

2 d]

UV-Index

Berlin 14 MED/d

Majorca 18 MED/d

Berlin Majorca Sydney

Sydney 23 MED/d

Equator 27 MED/d

Equator

SPF 30 Defines a relevant

Maximum of apre-Irradiation-Dose

on Earthfor

Photo-Stability-Testing

UVA-PF0 30 is more than enough



Using ISO 24443



Is there a reason to define a maximum pre-Irradiation Dose?

Proposal: If the calculated UVA-PF0-HDRS > 30

This value should be limited to UVA-PF0 = 30to calculate the pre-Irradiation Dose according to ISO 24443 (1.2 x UVA-PF0 [J/cm2])




No Irradiation of Skin



(and should be limited, correlated to UVA-PF0 30)


HDRS – Really non-invasive?

Is there a relevant irradiation dose during the measurement process?

Irradiation during measurement


HDRS – Erythemal weighted Irradiation Dose

UV-Range

[nm]

Mean Irradiation Dose(n=10)

[mJ/cm2]

Relative to Reference MEDu(Skin Type II, 21 J/cm2)

[%]

280 – 405

290 – 405

300 – 405

310 - 405

0.377 ± 0.029

0.336 ± 0.011

0.155 ± 0.009

0.036 ± 0.002

1.79

1.60

0.74

0.17








(Absolute no relevant UV-Irradiation of Skin)


Results / UVA-PF

Basic Ideas of HDRS

Technique


Results / UVA-PF



Summary


HDRS – Test-Design / UVA-PF

Experimental Design : Diffuse Reflectance Spectroscopy (DRS in vivo)

42 Products

UVA-PF 2 - UVA-PF 30

ISO 24442 (UVA-PF in vivo) ISO 24443 (UVA-PF in vitro)

210 Products

UVA-PF 2 - UVA-PF 50


HDRS – UVA-PF

Study Objective: Quantification of UVA-PF

UVA-PF =

P( ) I( ) 10 –A( ) d=320

=400

P( ) I( ) d=320

=400

P( ) = PPD Action SpectrumI( ) = Spectral Irradiance (UVA)A( ) = Absorbance


HDRS – Spectrum of UVA-PFHDRS

300 320 340 360 380 4000.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

DRS-Absorption

Wavelength [nm]

Abso

rptio

n [O

D]

Wavelength Range used for UVA-PFHDRS calculation

UVA-PF =

P( ) I( ) 10 –A( ) d=320

=400

P( ) I( ) d=320

=400

Direct calculation based on

in vivo DRS-Absorbance A( )


HDRS – Results UVA-PF24442 / UVA-PFHDRS

0 5 10 15 20 25 300

5

10

15

20

25

30

UVA-

PF [H

DRS]

UVA-PF [ISO 24442]

n=42

0 5 10 15 20 25 300

5

10

15

20

25

30

UVA-

PF [H

DRS]

UVA-PF [ISO 24442]

n=42

Linear Fit: m = 0.978 / R2 = 0.970


SPFHDRS – approved / UVA-PFHDRS – approved





(Absolute no relevant UV-Irradiation of Skin)


SPF

All comments can be adapted to UVA-PF

UVA-PF

Does it work in correlation to ISO 24443 UVA in vitro?


HDRS – Results UVA-PF24443 / UVA-PFHDRS

0 10 20 30 40 50 600

10

20

30

40

50

60

UVA-

PF [H

DRS]

UVA-PF [ISO 24443]

0 10 20 30 40 50 600

10

20

30

40

50

60

UVA-

PF [H

DRS]

UVA-PF [ISO 24443]

n=210

0 10 20 30 40 50 600

10

20

30

40

50

60

Linear Fit: m = 1.04 / R2 = 0.967

UVA-

PF [H

DRS]

UVA-PF [ISO 24443]

n=210


SPFHDRS – approved / UVA-PFHDRS – approved



SPF

All comments can be adapted to UVA-PF

UVA-PF

Correlation of UVA-PFHDRS to ISO 24442 (in vivo) and ISO 24443 (in vitro)


No Irradiation of Skin (Absolute no relevant UV-Irradiation of Skin)




Basic Ideas of HDRS

Technique


Results / UVA-PF



Summary


Are there any experimental differences for HDRS?

The actual method in Europe is still the COLIPA method from 2005(2x20min Spa Pool, static and wet SPF, calculation of WR)

HDRS – Water-Resistance-Testing


Water-Resistance-Testing

Product application 2.0 0.05 mg/cm2 Movement of water by jet impact, no air bubbles

Waiting Time 15 min Test area has to be totally covered with water / no contact to pool

1. Spa Pool Time 20 min Controlled water qualityEC Council Directive 98/83 EC

Drying Time at air 15 min Mg and Ca50 mg/ml - 500 mg/ml

1. Spa Pool Time 20 min Hygienic control by Cl

Drying Time at air 15 min / or until the test area is totally dryWater Temperature

29 2 °C.

Test of SPF on static and wet test areas



HDRS – Water-Resistance-Testing / Spa Pool




Are there any calculation differences for HDRS?


No!


SPFsi = individual SPF-staticSPFwi = individual SPF-wet%WRi = individual Water-Resistance in %mean %WR = Mean Water-Resistance in %d = 90% CI

%WRi = SPFwi - 1

SPFsi - 1 x 100

mean %WR = %WRi

n

n

i=1

HDRS – Water-Resistance-Testing / Calculation

mean %WR = mean SPFw - 1

mean SPFs - 1 x 100

mean SPFs = mean SPF-staticmean SPFw = mean SPF-wetmean %WR = Mean Water-Resistance in %

WR-Classic: WR-HDRS:

WRR = mean %WR – d






No!

Yes!

Are there any differences in the resulting WR for HDRS?


HDRS – Test-Design / Water-Resistance

Study Objective: Quantification of Water Resistance (WR)

Experimental Design: WR-Classic and WR-HDRS

Water Resistance: 2x20 min Spa Pool / WR: 30%-90% (classic)

Test Products : 15 Products

Measurements: DRS-static and DRS-wet

Analysis: Calculation of SPFHDRS / Calculation of WRHDRS


HDRS – Water-Resistance / Static Results

0 20 40 60 80 100 1200

20

40

60

80

100

120

SPFs

tatic

[HD

RS]

SPFstatic [ISO24444]

0 20 40 60 80 100 1200

20

40

60

80

100

120

SPFs

tatic

[HD

RS]

SPFstatic [ISO24444]

Linear Fit: m = 0.99 / R2 = 0.971


HDRS – Water-Resistance / Wet Results

0 20 40 60 80 100 1200

20

40

60

80

100

120

SPFw

et [

HDRS

]

SPFwet [ISO24444]

0 20 40 60 80 100 1200

20

40

60

80

100

120

SPFw

et [

HDRS

]

SPFwet [ISO24444]

Linear Fit: m = 1.11 / R2 = 0.951


HDRS – Water-Resistance / %-Results

0 20 40 60 80 100 1200

20

40

60

80

100

120

WR-

HDRS

[%

]

WR-classic [% ]

0 20 40 60 80 100 1200

20

40

60

80

100

120

WR-

HDRS

[%

]

WR-classic [% ]

Linear Fit: m = 1.07 / R2 = 0.942






No!

Yes!

Are there any differences in the resulting WR for HDRS? No!

Again -For the first time we have an alternative method which can handle WR-Testing!



Basic Ideas of HDRS

Technique


Results / UVA-PF



Summary


HDRS – Ring-Test / 3 Countries

1. Ringtest (2017): 1 Lab SPFISO 24444 3 Labs SPFHDRS7 Products SPF 5 – 30


5 10 15 20 25 30 35 40

5

10

15

20

25

30

35

40

Hybrid SPF = 1.00778 * (in vivo SPF)r2=0.96

Hybr

id SP

F

in vivo SPF

• Clinical Research Labs-CRL - Piscataway, US – SkinSkan (Horiba, USA)• Medcin Instituto da Pele - Guarulhos, BR – Fluorolog 3-22 (Horiba, USA) • Institut Dr. Schrader - Holzminden, GE – Bentham Instruments

HDRS – Ring-Test Results of 3 Labs / 7 Products (2017)




2. Ringtest (2018): 3 Labs SPFISO 24444 3 Labs SPFHDRS12 Products SPF 5 – 60


y = 1.0614xR² = 0.9917

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

0 10 20 30 40 50 60 70 80

HDRS

SPF

in vivo SPF

HDRS – Ring-Test Results of 3 Labs / 12 Products (2018)

12 Products

3 Labs / in vivo and HDRS

3 different Countries

Excellent Correlation




2. Ringtest (2018): 3 Labs SPFISO 24444 3 Labs SPFHDRS12 Products SPF 5 – 60

3. Ringtest (2019): 3 Labs SPFISO 24444 3 Labs SPFHDRS25 Products SPF 5 – 60 ISO Acceptance Criteria

Results ready for presentation on the next ISO-Meeting / June 2019


Basic Ideas of HDRS

Technique


Results / UVA-PF



Summary

Summary


ISO 24444 on its way to ISO 23698 (NWI)

Application

Test ProductIrradiation

of Test Product

SPFof

Test Product

Expected SPF Range

Volunteer recruitment

Definition of spectrum

Range finding

Definition of MED

Reading of MED

Waiting Time 16-24h

Energy - Homogeneity

Certificates

HDRSNon invasive

Measurement


SPFHDRS – The alternative non erythemal SPF – in vivo

No Ethical Concerns

Irradiation of Skin

Photostability linked to ISO 24443

SPF-Range covered up to SPF 120

Correlation of UVA-PF24442 / 3 and UVA-PFHDRS

Definition of MED

Training of MED reading

UVA-PF-Range covered up to UVA-PF 30

Not needed:

Information of expected SPF

Irradiation Spectrum

Excellent:


Let’s start and go this new way in SPF testing

Separate testing of SPF and UVA-PF

Correlation of SPF24444 and SPFHDRS

Water-Resistance Testing included


HDRS – ISO 23698

COLIPA-TF Sun Protection 1994 / Venice

ISO/TC217/WG7 Sun Protection test methods 2018 / Monaco

ISO 23698 / HDRSComing soon!

HDRS the first real changein SPF in vivo since 25 years!


Obrigado para sua atenção

Thank you for your attention

Merci de votre attention

Gracias por su atención

Vielen Dank für Ihre Aufmerksamkeit

Obrigado para sua atençãoo

Thank you for your attention

Merci de votre attention

Gracias por su atención

Headquarters - Holzminden

www.schrader-institute.dewww.schrader-institute.de

hdrs – colipa-tf sun protection 1994 / venice hdrs – the future of spf · 2019. 12. 29. ·...

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