Hybrid PMMA series UV Filters in PMMA Beads - … PMMA Beads … · When & How to incorporate Hybrid PMMA series? Q: When? A: After emulsion, after cooling down emulsion, incorporate

Hybrid PMMA series

UV Filters in PMMA Beads - Avobenzone - BEMT - EHT

Hybrid PMMA series

Core: Chemical UV Filters(30%) For UV protection

Shell: PMMA Bead(70%) 1) For Sensorial Modification 2) Oil soluble UV filters can be used into water phase

Hybrid AB Composition PMMA 70% Avobenzone* 30% Particle Size 5 um UVA Protection

Hybrid S Composition PMMA 70% BEMT** 30% Particle Size 5 um UVA+UVB

Hybrid EHT Composition PMMA 70% EHT*** 30% Particle Size 5 um UVB Protection

*Avobenzone: Butyl Methoxy dibenzoylmethane(BMDBM)

**BEMT: bis-ethylhexyloxyphenol methoxyphenyl triazine

***EHT: Ethyl Hexyl Triazone

When & How to incorporate Hybrid PMMA series?

Q: When? A: After emulsion, after cooling down emulsion, incorporate Hybrid PMMA

at low temperature(i.e. <30℃)

Q: Why? A: As the Melting point of BMDBM is 81~86℃, if Hybrid AB adds before

emulsion, during the emulsion process, the emulsion temperature could go up more than 81℃, BMDBM becomes liquid and it would be leaked out from PMMA shell.

Q: How to add? A: Polymer Micro Beads are slightly hydrophobic, it would be difficult to

incorporate polymer beads directly into water especially without poly alcohols Thus, premix polymer beads in poly alcohol solutions such as 1,3 Butylene Glycol or Propylene Glycol or Glycerin and add the premixed phase after emulsion

Melting point BMDBM: 81~86℃ BEMT: 80 ℃ EHT: 123 ℃

Hybrid AB

Water dispersible

UVA filter

Copyright © 2014 by SUNJIN Chemical Co. LTD ALL RIGHTS RESERVED. 4

Hybrid AB










The amount of BMDBM decreases

weakening of the UVA protection

(3) Poor Compatibility

(2) Poor Photo-stablility

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

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

(1) Poor Solubility

BMDBM(=Avobenzone) is a great UVA filter but has Problems too

INCI Name Trade Name USA Japan EU Australia

BMDBM Parsol 1789 3 10 5 5

However, BMDBM is globally approved

Problems

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

6 Big Things about Hybrid AB

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






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

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

Hybrid PMMA Bead

Big Thing #2






6. Novel formula


PA+++ system

Product % needed for PA+++

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 BMDBM

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

*DHHB Diethylamino hydroxybenzoyl hexyl benzoate **BEMT bis-ethylhexyloxyphenol methoxyphenyl triazine

To achieve PA+++,

Avobenzone 3.5% in oil

phase Possible option?

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

Difficult to use Avobenzone

3.5% in oil phase.

The reasons are…

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

Oil Phase

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 - - - -

BEMT 4 5

Water Phase

HYBRID AB - 6 - 6 6 - - -

Amount of BMDBM

3 3

=1.2+6%*30%

3 3

=1.2+6%*30%

3.5 =1.7+6%*

30%

3.5 - -

In vivo PFA 7.0 7.0 7.2 8.0 8.0 8.0 8.0 9.2

Recommendation from SUNJIN


Global PA+++ solution


Chemical Filter Only SPF50 PA+++


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

Big Thing #3






6. Novel formula



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

Good Spread & Feel due to silica shell

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

Solubility ratio

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

frequently used as a texture additive, and therefore lend the formula

a soft-touch effect

Big Thing #4






6. Novel formula


Theoretical Explanation

Photo-degradation of Avobenzone

can be blocked as Avobenzone is

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

5um PMMA Bead With BMDBM

‘Hybrid PMMA bead containing chemical Sunscreen filters’ Sung-HO Lee, SUNJIN Chemical IFSCC 2008


Photo-stability Test protocol

Proposed protocol for determination of photostability Part I: cosmetic UV filters

Colipa Method

PMMA Plate 5cm2

Layer 1.3mg/cm2

30min drying

Analsis of solution: HPLC

Irradiation 10MED


Photostability Test Result

3.0 2.95

10 MED

3.0

2.1 10 MED

3.0

2.7

10 MED

3.0 2.95

10 MED

Hybrid AB 10% BMDBM 0% OMC 7.5% OS 5% OC 0% BEMT 0% Initial Net BMDBM = 3% Photo-stable

Hybrid AB 0% BMDBM 3% OMC 7.5% OS 5% OC 0% BEMT 0% Initial Net BMDBM = 3%

Hybrid AB 0% BMDBM 3% OMC 7.5% OS 5% OC 2.4% BEMT 0% Initial Net BMDBM = 3%

Hybrid AB 0% BMDBM 0% OMC 7.5% OS 5% OC 0% BEMT 3% Initial Net BMDBM = 0% Net BEMT = 3% Photo-stable

Big Thing #5






6. Novel formula


Minimized Skin Irritancy

#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

Sample size: 5 subjects(Korean) Study Design: Patch test Application time: 72hr Dosage: 25㎕

Dermal response: 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

Minimized Skin Irritation

Test Condition:

Test Results

The encapsulation of UV filters

inside PMMA bead reduces

dermal uptake, thereby reducing

the potential for irritation

Big Thing #6






6. Novel formula


Example 1: Mousse Foundation with UVA protection

25

No. Trade Name INCI %

A

1 SUNTITAN-AS Titanium dioxide & Triethoxycaprylyl silane

7.00

2 SUNSERI-AS Sericite & Triethoxy caprylyl silane 5.00

3 SUNMICA-AS Mica & Triethoxycaprylyl silane 2.00

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 PMMA & Avobenzone 5.00

8 SUNIOR-AS Iron oxide Red & Triethoxycaprylyl silane

0.42

9 SUNIOY-AS Iron oxide Yellow & Triethoxycaprylyl silane

0.84

10 SUNIOB-AS Iron oxide Black & Triethoxycaprylyl silane

0.05

B

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 3.00

C 21 KSG 16 Dimethicone / Vinyl Dimethicone Cross Polymer

30.00

D 22 FRAGRANCE FRAGRANCE 0.08

SJF-0806-Mousse Foundation-ver2.0

Have you ever seen any

mousse foundation with

UV protection property? Difficult to see in the market, right?

Most chemical UV filters are

not very silicone-compatible.

How to incorporate silicone-

incompatible UV filters into

silicone phase?

You can incorporate Hybrid PMMA into silicone gel phase very easily by simple mixing

Evaluation

SPF 50

PA ++(5.0)

SPF/UVA

Critical Wavelength

White Index

Sensory Index


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

Hybrid S

BEMT in PMMA Beads Water dispersible UVA & UVB filter


Hybrid S










BEMT

• INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine(BEMT)

• oil-soluble

• Broad-spectrum UV absorber, absorbing UVB as well as UVA

rays. It has two absorption peaks, 310 and 340 nm.

• Highly photostable. Even after 50 MEDs (minimal erythemal

doses), 98.4% remains intact. It helps prevent the

photodegradation of other sunscreen actives like avobenzone

• Not approved in US

• Unlike some other organic sunscreen actives, it shows no

estrogenic effects in vitro.[12]

• A recent development is Tinosorb S Aqua, which is

bemotrizinol in a PMMA matrix dispersed in water. This makes

it possible to add bemotrizinol to the water phase

Can’t be used together with more than 3% of cyclomethicone(D5) in formulation

BEMT needle form crystal

6 Big Things about Hybrid S


2. SPF50 & PA+++




6. Novel formula


Hybrid EHT

EHT in PMMA Beads Water dispersible UVB filter


Hybrid EHT










EHT

(1) Poor Solubility Bad Things (2) Crystallization

EHT is susceptible

to crystallization that results in loss of product

aesthetics, sun protection,

appearance, stability

PPG-3 myristyl ether 13.0

Polyol-fatty acid ester 10.0

Triethyl citrate 9.0

Caprylic/capric acid triglycerides 4.0

C12C15-alcohol benzoate 4.0

Isopropyl myristate 3.5

Isopropyl palmitate 2.0

Oleic acid decyl ester 1.5

2-Ethylhexanoic acid cetylstearyl ester 1.0

Olive oil 1.0

Peanut oil 1.0

Jojoba oil < 1.0

Propylene glycol < 1.0

Liquid paraffin < 1.0

INCI: Ethylhexyl triazone • The most powerful and photostable UVB filter

• Excellent photostability

• EHT, oil soluble UVB filter is the most powerful of its

kind and has the highest UV absorption

Good Things

Globally Approved: EU(5%),

Japan(3%), Australia(5%),

Korea(5%)

3 Big Things about Hybrid EHT

1. Water dispersible UVB filter

2. Suitable High SPF



Hybrid PMMA series UV Filters in PMMA Beads - … PMMA Beads … · When & How to incorporate Hybrid PMMA series? Q: When? A: After emulsion, after cooling down emulsion, incorporate

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