Hybrid AB
Water dispersible
UVA filter
Hybrid AB
Core: Chemical
For UV protection
UV Filters(30%)
Shell: PMMA Bead(70%)
1) For Sensorial Modification
2) Oil soluble UV filters can be used into water phase
Hybrid AB
Hybrid S
Hybrid EHT
Composition
PMMA
70%
*
Avobenzone 30%
Composition
PMMA
70%
**
BEMT
30%
Composition
PMMA
70%
***
EHT
30%
Particle Size
5 um
Particle Size
5 um
Particle Size
5 um
UVA Protection
UVA+UVB
UVB Protection
*Avobenzone:
Butyl Methoxy
dibenzoylmethane(BMDBM)
**BEMT:
bis-ethylhexyloxyphenol
methoxyphenyl triazine
***EHT:
Ethyl Hexyl Triazone
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
1
BMDBM(=Avobenzone)
UVA filter
is a great
but has
Problems too
Problems
(1) Poor Solubility
Avobenzone
•
•
•
•
INCI: Butyl Methoxy
dibenzoylmethane(BMDBM)
Oil soluble UVA filter
Avobenzone was patented in
1973 and was approved in
the EU in 1978. It was
approved by the FDA in 1988.
Its use is approved
worldwide
Avobenzone is sensitive to
the properties of the solvent,
being relatively stable in
polar protic solvents and
unstable in nonpolar
environments
(3) Poor Compatibility
Dimethicone
0
3
Cyclomethicone
0
50
Mineral oil
1
50
Isostearyl Isosterate
3
50
Octylpalmitate
3
50
Capric/Caprylic 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
The amount of BMDBM decreases
 weakening of the UVA protection
Aluminum oxide is one of the most
common coating material for TiO2.
BMDBM forms a complex with Al3+
salts from TiO2 coatings
(4) Crystallization
BMDBM is susceptible to
crystallization that results in loss of
product aesthetics, sun protection,
appearance, stability
(2) Poor Photo-stablility
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.
However, BMDBM is globally approved
INCI Name
Trade Name
USA
Japan
EU
BMDBM
Parsol 1789
3
10
5
Australia
5
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
2
6 Big Things about Hybrid AB
Hybrid AB
Composition
PMMA
70%
*
Avobenzone 30%
Particle Size
5 um
UVA Protection
1. Water dispersible UVA filter
2. Global PA+++ solution
3. Ultra Light Texture
4. Improved photo-stability
5. Minimized Skin Irritancy
6. Novel formula
Big Thing #1
1. Water dispersible UVA filter
2. Global PA+++ solution
3. Ultra Light Texture
4. Improved photo-stability
5. Minimized Skin Irritancy
6. Novel formula
UVA filter in water phase
Most UV filters are either oils or need to be dissolved in polar emollients.
The results are highly loaded oil phases, which lead to the most common limitations in
Sun Care formulations
- Reduced cosmetic elegance
- Lower flexibility to modify the sensory properties of formulations
- Suboptimal performance due to the use of filters mainly in one formulation phase
Hybrid PMMA, water dispersible, can be incorporated in the water phase
Hybrid
PMMA
Bead
The use of Hybrid PMMA allows a balanced incorporation of UV filters in the water
and oil phase. Therefore, a more homogeneous distribution of the UV filters on
skin can be achieved which often result in a boosting effect
Through incorporation into water phase, Hybrid PMMA offers increased
formulation flexibility. Lower UV filter concentration is needed in the oil phase to
achieve highest contribution to SPF and UVA-PF
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
5
Big Thing #2
1. Water dispersible UVA filter
2. Global PA+++ solution
3. Ultra Light Texture
4. Improved photo-stability
5. Minimized Skin Irritancy
6. Novel formula
PA+++ system
Product
Diethylamino hydroxybenzoyl
hexyl benzoate
Approval Status
(max%)
Remark
EU
JP
US
AUS
DHHB*
4%
10
10
-
10
Not approved in US
Expensive
BEMT**
4%
10
3
-
10
Not approved in US
Expensive
Avobenzone
3.5%
5
10
3
5
Globally approved
Zinc Oxide
(40nm)
17%
25
100
25
20
<100nm ZnO is not
listed as UV Filter in
EU
BMDBM
*DHHB
%
needed
for
PA+++
To achieve PA+++,
Avobenzone 3.5% in oil
phase Possible option?
**BEMT
bis-ethylhexyloxyphenol
methoxyphenyl triazine
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
7
Difficult to use Avobenzone
3.5% in oil phase.
The reasons are…
W/Si
 Not possible

As avobenzone is not soluble to silicone oils, usage of even
small amount of avobenzone together with silicone oils causes
sever formula instability
O/W
 Not recommended
to put 3.5% of Avobenzone
into internal oil phase as it greatly restricts formulation
freedom in oil phase
W/O
 Putting 3.5% in external oil phase is possible…
 Concerns about photostability & solubility of Avobenzone
requires use of Octocrylene and other heavy oils
 So the feel is very oily and unpleasant
So…Hybrid AB in water phase!
Global PA+++ solution
O/W
#1-1
#1-2
#2-1
#2-2
#3-1
#3-2
#4-1
#4-2
BMDBM
(=avobenzone)
3
1.2
3
1.2
1.7
3.5
-
-
Octocrylene
1
1
1
1.0
1.0
1
-
-
benzophenone-3
-
-
3
3
-
-
-
-
4
5
-
-
-
3.5
-
-
8.0
8.0
9.2
Oil Phase
BEMT
Water Phase
HYBRID AB
-
6
Amount of
BMDBM
3
=1.2+6%*
30%
3
In vivo PFA
7.0
7.0
7.2
3
-
6
6
3
3.5
8.0
8.0
=1.2+6%* =1.7+6%*
30%
30%
Recommendation from SUNJIN
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
9
Global PA+++ solution
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
10
Chemical Filter Only SPF50 PA+++
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
11
PA+++ solution for USA
Max approval % of
avobenzone in USA is 3% as
compared to 5% or more in
other countries
From the formula right,
BMDBM 1.2% +
Hybrid AB 6%
= 1.2% + 6%*30%
= 1.2% + 1.8%
= 3.0%
BMDBM 3% is not enough to
achieve PA+++
So that’s why BPS-3 is used
to achieve PA+++
No mineral filters used to
meet FDA regulation
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
12
Big Thing #3
1. Water dispersible UVA filter
2. Global PA+++ solution
3. Ultra Light Texture
4. Improved photo-stability
5. Minimized Skin Irritancy
6. Novel formula
3. Ultra Light Texture
Good Spread & Feel due to silica shell
5um PMMA Bead
With BMDBM
Hybrid AB is Spherical. You can feel only
external PMMA Bead
Ultra Light Texture
No need to use emollients to solubilize
BMDBM
Solubility ratio
Dimethicone
0
3
Cyclomethicone
0
50
Mineral oil
1
50
Isostearyl Isosterate
3
50
Octylpalmitate
3
50
Capric/Caprylic Triglyceride
7
50
Isopropyl Myristate
9
50
PG/Dicaprate/Dicaprylate
5
50
C12-C15 Alkyl Benzoate
11
50
Octyldodecanol
13
50
frequently used as a texture additive, and therefore lend the formula
Ethyl Butylacetylaminopropionate
26
50
a soft-touch effect
 Most chemical filters are very oily and leave behind an unpleasant,
sometimes sticky feel on the skin
 Hybrid PMMA has the excellent skin feel of PMMA bead which is
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
14
Big Thing #4
1. Water dispersible UVA filter
2. Global PA+++ solution
3. Ultra Light Texture
4. Improved photo-stability
5. Minimized Skin Irritancy
6. Novel formula
Theoretical Explanation
Photo-degradation of Avobenzone
can be blocked as Avobenzone is
5um PMMA Bead
With BMDBM
immobilized or located inside solid
PMMA matrix where avobenzone is
segregated or protected from other
UV filters or any other kinds of
potentially reactive chemicals
Thus Hybrid PMMA system is very
novel and innovative way to improve
photo-stability of avobenzone
‘Hybrid PMMA bead containing chemical
Sunscreen filters’
Sung-HO Lee, SUNJIN Chemical
IFSCC 2008
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
16
Photo-stability Test protocol
Colipa Method
Irradiation
10MED
Proposed protocol for
determination of
photostability Part I:
cosmetic UV filters
PMMA Plate 5cm2
Layer 1.3mg/cm2
30min drying
Analsis of solution:
HPLC
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
17
Photostability Test Result
3.0
2.95
10
MED
3.0
3.0
3.0
2.95
2.7
10
MED
2.1
10
MED
10
MED
Hybrid AB
BMDBM
10%
0%
Hybrid AB
BMDBM
0%
3%
Hybrid AB
BMDBM
0%
3%
Hybrid AB
BMDBM
0%
0%
OMC
OS
OC
7.5%
5%
0%
OMC
OS
OC
7.5%
5%
0%
OMC
OS
OC
7.5%
5%
2.4%
OMC
OS
OC
7.5%
5%
0%
BEMT
0%
BEMT
0%
BEMT
0%
BEMT
3%
Initial
Net BMDBM = 3%
Photo-stable
Initial
Net BMDBM = 3%
Initial
Net BMDBM = 3%
Initial
Net BMDBM = 0%
Net BEMT = 3%
Photo-stable
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
18
Big Thing #5
1. Water dispersible UVA filter
2. Global PA+++ solution
3. Improved photo-stability
4. Ultra Light Texture
5. Minimized Skin Irritancy
6. Novel formula
Minimized Skin Irritancy
Test Results
#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
The encapsulation of UV filters
inside PMMA bead reduces
dermal uptake, thereby reducing
the potential for irritation
Minimized Skin Irritation
Dermal response:
Test Condition:
Sample size:
Study Design:
Application time:
Dosage:
5 subjects(Korean)
Patch test
72hr
25㎕
0 = No evidence of irritation
1 = Minimal erythema,
2 = Readily visible erythema,
3 = Erythema and papules
4 = Definite edema
5 = Erythema, edema, and papules
6 = Vesicular eruption
7 = strong reaction spreading
“The
500-Da rule for skin
penetration is: 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: 310.4
OMC Mw: 290
Octocrylene Mw: 361
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
20
Big Thing #6
1. Water dispersible UVA filter
2. Global PA+++ solution
3. Improved photo-stability
4. Ultra Light Texture
5. Minimized Skin Irritancy
6. Novel formula
Example 1: Mousse Foundation with UVA protection
SJF-0806-Mousse Foundation-ver2.0
Evaluation
No.
Trade Name
INCI
%
SPF
50
1
SUNTITAN-AS
Titanium dioxide & Triethoxycaprylyl
silane
PA
++(5.0)
2
SUNSERI-AS
Sericite & Triethoxy caprylyl silane
5.00
SPF/UVA
3
SUNMICA-AS
Mica & Triethoxycaprylyl silane
2.00
Critical
Wavelength
4
SUNSIL-130HSC
Silica & Methicone
5.00
5
SUNSIL Tin50
Silica & Titanium dioxide
3.50
6
Hybrid Talc(DM)
Talc & MBBT & Dimethicone
5.00
7
Hybrid AB
5.00
8
SUNIOR-AS
9
SUNIOY-AS
10
SUNIOB-AS
PMMA & Avobenzone
Iron oxide Red & Triethoxycaprylyl
silane
Iron oxide Yellow & Triethoxycaprylyl
silane
Iron oxide Black & Triethoxycaprylyl
silane
11
SALACOS 99
Isononyl isononanoate
10.00
12
DC200-10CS
Dimethicone
5.00
13
SQUALANE
Squalane
3.00
14
IPP
Isopropyl Palmitate
2.00
15
L.P
Liquid Paraffin
6.00
16
NOMKORT HKG
Glyceryl Behenate / Elcosadioate
4.00
17
JOJOBA OIL
Jojoba oil
1.00
18
VIT.E ACETATE
Tocopheryl Acetate
0.20
19
PARSOL MCX
Ethylhexyl Methxycinnamate
2.00
20
GRAPE SEED OIL Grape Seed Oil
C
21
KSG 16
Dimethicone / Vinyl Dimethicone Cross
Polymer
30.00
D
22
FRAGRANCE
FRAGRANCE
0.08
White Index
A
Sensory Index
Most chemical UV filters are
not very silicone-compatible.
How to incorporate siliconeincompatible UV filters into
silicone phase?
B
7.00
0.42
0.84
0.05
Have you ever seen any
mousse foundation with
UV protection property?
Difficult to see in the market,
right?
You can incorporate Hybrid
PMMA into silicone gel
phase very easily by simple
mixing
3.00
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
22
More Examples:
Formulation Tip
Hybrid AB provides UVA protection from water phase
5% of Hybrid AB can go up to PA++
Examples
Sun Protect Gel, go page 142
Sun Spray, go page 139
Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED.
23