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L A M B I O T T E & C I E S . A .

AcetalsAcetals in Cosmetics

Lambiotte & Cie started its activities in 1860 with forestry and sawmill exploitation,

producing railway sleepers. In a desire to increase the value of its wood waste

production, the company adopted an innovative carbonization process to convert

wood to charcoal. One of the chemical by-products of this distillation technology was

methanol. From 1901, Lambiotte’s interest in chemicals grew with the production of

formaldehyde from wood methanol. By 1970, Lambiotte’s passion for chemistry led to

the use of formaldehyde as a reagent in the production of acetals and hemicetals. Since

then, the company has continued to develop its expertise in production technologies,

making it a leader in the highly specialised field of acetals synthesis.

We at Lambiotte are proud to offer a wide range of industrial acetals, manufactured

with state-of-the-art equipment in a continuous process reaction. Our precision and

technical expertise in this specialist field guarantees the highest and most constant

quality and purity of product, allowing us to respond to each specific demand for

synthesis of acetals and chemical derivates from aldehydes and/or alcohols.

A dedicated support team is available to give the customer technical advice, providing

tailored formulae for many industrial sectors. In order to meet the customer’s needs,

we propose the services of our application laboratories in aerosols, cosmetics, coatings...

to develop customised formulae. Indeed, every department in Lambiotte, be it production,

quality control, sales, marketing, logistics or accounting is dedicated to customer satisfaction.

A world-wide network of specialised distributors ensures fast product availability,

delivery, and technical support to guarantee optimal client services.

L a m b i o t t e & C i e

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Do you want to answer the future VOC regulations ?Do you want to improve the spray quality of hair sprays ?Do you want to spray a sun care product ?Do you want to improve the drying of cosmetic sprays ?Do you want to confer a fresh feeling to your cosmetics ?

METHYLAL IS THE ANSWER TO YOUR REFORMULATION NEEDS Methylal (INCI) helps the formulator to answer the new requirements of the European regulation, through its extremely low toxicity, the absence of allergenic impurities and its solvent power.

Acetals, Methylal (inci) and 1,3- Dioxolane (inci), have all the following general characteristics :

• not mutagenic• not carcinogenic• not toxic for reproduction• absence of allergic reactions (absence of impurities)• not dangerous to the environment• biomimetic• amphiphilic

Methylal shows all its benefits in aerosols and pump sprays.

For aerosols, Methylal can be used with all propellants such as :Propane, Butane, Isobutane, Dimethyl Ether (DME), HFA and also with compressed gases such as CO2

Acetals find applications in the following cosmetics :

Hair Care (Hair spray, Hair mousse, Hair gel, Ethnic products) Skin Care (Sun and After Sun Care, Body Care (cream, milk, oil and gel)) Toiletries (Body deodorants and Body Splash (alcohol free), Wet wipes) Colour Cosmetics (Nail varnishes and Cleaners) Parapharmaceuticals

Hair Care 4

Skin Care 9

Toiletries 12

Nail Varnishes 14

Parapharmaceuticals 14

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HAIR SPRAY

AEROSOL

- Classic

- Low VOC

• Anhydrous 55%VOC with 152A

• Water based 55% VOC with DME

PUMP

- Classic

- Low VOC

Advantages of using Methylal :

- Powerful solvent for resins and actives (such as vitamins, silicones, UV filters, perfume...)

- Fast drying

- Reduction of the particle size

- Low VOC (compatibility with water, with HFA...)

CLASSICAL FORMULATION OF HAIR SPRAY :

HS 24 B is a classic Ethanol based formula

HS 24 A is made with 50 % Ethanol and 50 % Methylal

H a i r C a r e

HS 24 A

% weight

HS 24 B

% weight

6.02 Luviskol va 37 hm 6.02

0.07 Dow fluid 344 0.07

0.07 Freshlon fragrance 0.07

31.92 Ethanol 63.84

31.92 Methylal /

30.00 Propane-butane 3.2 bar 30.00

100.00 100.00

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METHYLAL SHORTENS THE DRYINg TIME

A practical test* with hair spray HS 24 B and A (Ethanol- and Methylal-based) shows the following :

(*Half head study by Hazel Pool UK in June 1996 (panel))

Methylal reduces the drying time from 67 seconds to 23.5 seconds in salon conditions

(average time, dry state appreciated by the panel)

METHYLAL REDUCES THE PARTICLES SIzE

0

10

20

30

40

50

60

70

Time

(sec)

Average drying time on various hair types

HS 24 B

HS 24 A

Time(sec)

70

60

50

40

30

20

10

0

HS 24 B

HS 24 A

0

10

20

30

40

50

60

70

80

90

HS 24 A HS 24 B

Particle size (µm)

dv (0.1)

dv (0.5)

dv (0.9)

90

80

70

60

50

40

30

20

10

0HS 24 A HS 24 B

dv (0.1)

dv (0.5)

dv (0.9)

Particule size (µm)

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METHYLAL REDUCES THE PARTICLES SIzE

The substitution of Ethanol by Methylal improves significantly the spray quality:

- reduction of the average particle size : 18 microns

- improvement of the particle size homogeneity : smaller size difference between the biggest particles

(vol. med. 90%) and the smallest particles (vol. med. 10%).

METHYLAL IMPROvES THE gLOBAL qUALITY OF HAIR SPRAYS

Drying quality evaluation from panel (half head test)

H a i r C a r e

Particle size (µm)

0 10 20 30 40 50 60 70 80 90

100

0,00% 15,96% 31,92% 47,88%

% Methylal in the formulation

propellant excluded

dv (0.5) dv (0.1)

dv (0.9) Particle size (µm)

100

90

80

70

60

50

40

30

20

10

0

dv (0,9)

dv (0,5)

dv (0,1)

0,00% 15,96% 31,92% 47,88%

% Methylal in the formulation propellant excluded

010203040506070

8090

100

Quote/100

Drying Quality evaluation from panel (half head test)

HS 24 A

HS 24 B

Quote / 100

100

90

80

70

60

50

40

30

20

10

0

HS 24 A

HS 24 B

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55% vOC HAIR SPRAY (WATER AND DME BASED)

METHYLAL REDUCES THE PARTICLES SIzE OF 55% vOC HAIR SPRAYS

HS 55/40 A

% weight

HS 55/40 B

% weight

8.00 Aquaflex FX64 8.0

30.0 Water 30.0

10.0 Acetone 10.0

10.0 Ethanol 22.4

12.4 METHYLAL /

0.4 Univul MS40 0.4

0.2 DL Panthenol 0.2

29.00 DiMethylEther 29.00

100.00 100.00

0

100

200

300

400

500

600

HS 55/40 A HS 55/40 B

Particle Size (µm)

dv (0.1)

dv (0.5)

dv (0.9)

600

500

400

300

200

100

0HS 55/40 A HS 55/40 B

dv (0.1)

dv (0.5)

dv (0.9)

Particule size (µm)

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80% vOC PUMP SPRAY

METHYLAL ALSO REDUCES THE PARTICLE SIzE OF PUMP SPRAYS

HAIR MOUSSEAdvantages of using Methylal :

- Improvement of the foam expansion and stability

- No defoaming thanks to its lower polarity compared to alcohols

- Excellent solubiliser of the resins for styling mousses

- Faster drying time of the hair styling mousses

HAIR gELAdvantages of using Methylal :

- Powerful solvent of actives (such as resins, vitamins, UV filters, perfume...)

- Faster drying

H a i r C a r e

SAMPLE N° % weight A B C D

Advantage CP 10 10 10 10

AMP 100 0,21 0,21 0,21 0,21

Surfadone LP 300 0,1 0,1 0,1 0,1

Perfume 0,2 0,2 0,2 0,2

METHYLAL 0 10 20 30

Ethanol 74,8 64,8 54,8 44,8

Water 14,69 14,69 14,69 14,69

% Methylal

Particle size (µm)

0 10 20 30

40 50

60 70 80

90 100

0 5 10 15 20 25 30

% Methylal

Average particle size

d(v,0.9)

d(v,0.1)

Sample A B C D

Particle size (µm)

100

90

80

70

60

50

40

30

20

10

0

d(v,0.9)

Average particle size

d(v,0.1)

0 5 10 15 20 25 30

A B C DSample

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MILK AND CREAMMethylal presents interesting amphiphilic properties for cosmetic formulations.

It can be used in oil-in-water as well as in water-in-oil emulsions, in water-based and oil-based gels,

in skin tonics and rinse-off products.

OIL-IN-WATER EMULSIONS

Methylal adds a strong refreshing sensation to milks and creams.

With its water miscibility, high level of hydrogen bounding and its boiling point of 42°C (108°F),

Methylal guarantees a nice refreshing feeling in oil-in-water milks and creams.

To substitute cyclomethicone, it is interesting to use it together with dimethicone or dimethiconol,

both being very soluble in Methylal.

Methylal is amphiphilic and neither narrows the HLB range of requested emulsifiers,

nor changes the oil-in-water concentration range for certain emulsifier systems.

WATER-IN-OIL EMULSIONS

These are interesting for sun creams and milks, giving a soft cooling sensation due

to the occlusive effect of the oil phase in contact with skin.

Here again, Methylal shows its extremely strong cooling effect, which is interesting considering

the fact that sun products often require a strong refreshing sensation.

Furthermore, Methylal allows the use of non predispersed inorganic filters (TiO2),

which allows the reduction of the formulation costs. Methylal also solubilises some

of the surfactants used for those emulsions.

Methylal will of course be used preferably in cold processed dispersion

(otherwise it can be incorporated after cooling).

WATER-BASED gELS

Methylal shows an extremely wide compatibility with all thickeners :

acrylics, cellulose derivatives, etc.

Methylal confers also a nice effect to those formulae.

OIL gELS

Methylal decreases the strong greasy impression that these gels can give.

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RINSE-OFF PRODUCTS

A clear gel shampoo can easily be formulated with Methylal, improving the cleaning power.

In other formulations, Methylal can be used to achieve an exceptional oil solvency.

SUN CARE AND AFTER SUN CARE

Methylal showing amphiphilic properties can be incorporated in O/W and W/O emulsion

as well as in water and lipo gels

Methylal offers several advantages. It is :

- an excellent disperser for micronised TiO2

- by far the best solubiliser for all organic filters, cinnamates…, benzophenone,

and also for the most difficult to solubilise :

• Ethylhexyl triazone (solubility limit 13% w/w at 20°C)

• Butyl methoxy dibenzoyl methane (soluble up to 35% w/w)

- easy to emulgate

- lowering the viscosity of oils or emulsions

- conferring a nice fresh feeling to the product

Example of formula :

Sun Mousse, Sun oil, Sun Water, Emulsion...

BIOLOgICAL PRESERvATION

Methylal allows the reduction of the preservative concentration for the same biological protection

of the preparation (in the same way as Ethanol)

Using formula of sun milk 1 (SPF 7)

Challenge test following the European Pharmacopea on strains :

- Staphilococcus aureus

- Pseudomona acriginosa

- Enterococcus hirae

- Candida albicans

- Aspergilus niger

Log reduction comparison

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Parasure : Phenoxyethanol and Parabens

Test confirmed by other challenge tests. No preservative required if > 4 % Methylal in O/W emulsion

If fungi : Aspergilus niger added strain, No preservative required if > 8 % Methylal in O/W emulsion

Challenge tests on O/W emulsion

% FOR. A FOR. B FOR. C FOR. D FOR. E FOR. F FOR. G FOR. H FOR. I

SEPIGEL 305 3,2 3,2 3,2 3,2 3,2 3,2 3,2 3,2 3,2

WATER 81,95 77,95 73,95 81,45 77,45 73,45 80,95 76,95 72,95

METHYLAL 0 2 4 0 2 4 0 2 4

1,4 BUTANEDIOL 4 4 4 4 4 4 4 4 4

EDTAdiNa 0 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05

PARASURE 0 0 0 0,2 0,2 0,2 0,4 0,4 0,4

VIT E 0,5 0,5 0,5 0,5 0,5 0,5 0,5 0,5 0,5

ISOSTISO. 5 5 5 5 5 5 5 5 5

METHYLAL 0 2 4 0 2 4 0 2 4

PARASURE 0 0 0 0,3 0,3 0,3 0,6 0,6 0,6

DVD VC I10 3 3 3 3 3 3 3 3 3

MACADAMIAOIL 2 2 2 2 2 2 2 2 2

Fragrance 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3

0

1

2

3

4

5

6

7

Form A Form B Form C Form D

Challenge test

log reduction at 28 day s

Staphilo aureus

Pseudo aeruginosa

Entero Hirae

Candida albicans

Aspergilu niger

7

6

5

4

3

2

1

0Form A

Challenge test : log reduction at 28 days

Form B Form C Form D

Staphilo aureus

Pseudo aeruginosa

Entero Hirae

Candida albicans

Aspergilu niger

A B C D E F G H I

STAPHILO AUREAUS + + + + + + + + +

PSEUDOMONAS AERUGINOSA - + + + + + + + +

CANDIDA ALBICANS - + + + + + + + +

ASPERGILUS NIGER + + + + + + + + +

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DEODORANT

AEROSOL

- Alcohol free deodorant

- Non flammable aerosol deodorants (CO2)

Methylal allows the filling with CO2 and improves the spray quality.

It makes it easier to fill with CO2 and with 40% of Methylal into the formula,

you get the same spray quality as with propane/butane

PUMP

- Alcohol-free pump deodorants (water-based).

With Methylal it is easy to formulate alcohol free deodorants reducing the skin irritation

and photosensitization

Tanks to its amphiphilic character, Methylal is a good solvent for perfumes and therefore

permits to use less emulsifier and surfactant solubiliser

WATER BASED PUMP DEODORANT

t o i L e t r i e S

A

% weight

B

% weight

75 Water 75

18.6 Methylal /

/ Ethanol 18.6

3 Sorbitol 3

3 Tween 20 3

0.25 Germall 115 0.25

0.15 Fragrance 0.15

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Drying time of pump spray deodorant

BODY CARE

Methylal is a good solvent for lipophilic ingredients such as vitamins, essential oils, perfume….

therefore less emulsifier is needed.

Thanks to its fast evaporation, Methylal gives a cooling and refreshing effect on the skin.

Example of formula :

- Body Splash

- Tonic

- Lotion

WET WIPES

Methylal is more and more used in formulations of wet wipes.

Its cooling effect is especially suitable to replace alcohol and to avoid allergenic reactions.

It help to formulate a wide range of cosmetics wet wipes:

- Refreshing wipes

- After Shave wipes

- Cleansing wipes

- Etc.

Methylal is an adapted and innovative answer for those added value products.

0

50

100

150

200

250

300

Time (sec)

Formulation A Formulation B

Drying time of pump spray deodorant

Time (sec)

300

250

200

150

100

50

0Formulation A Formulation B

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Acetals used : Methylal and Dioxolane

Advantages :

Methylal :

- substitute for toluene, acetone

- improves the drying

- development of water-based formulations

Dioxolane :

- solubiliser of PU resins (peelable)

- solubiliser of acrylic resins

- powerful cleaner

Suggested formulations :

- nail varnish

- removers - water-based

- two phases removers water based

- wet wipe removers

- Freezing spray

- Haemostatic spray

- Plaster spray

- Insect repellent

- Etc.

FREEzINg SPRAY (MUSCULAR DECONTRACTINg SPRAY)

Through its high evaporation rate, Methylal emphasises the cooling effect.

This formula can be packaged in a pump or an aerosol.

Aerosols with propane butane and other propellants.

Thanks to its high Bunsen coefficient, Methylal can be easily filled with CO2.

n a i L V a r n i S H e S

Ingredient % Function

Methylal 60 Solvent - cooling feeling

Ethanol 36,5 Solvent

Camphor 1,5 Denaturating agent

Menthol 1,5 Denaturating agent

Methyl salicylate 0,5 Analgesic agent

CAS : 119-36-8

Total 100

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LUXEMBOURG

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o f f i C e S • b r u S S e L SAvenue des Aubépines 18B-1180 BrusselsBelgiumTel: +32 2 374 44 65Fax: +32 2 375 31 55E-mail: info@lambiotte.comWeb site: www.lambiotte.com

P L a n t • m a r b e H a nGrand’Rue 79B-6724 MarbehanBelgiumTel: +32 63 41 00 80Fax: +32 63 41 16 98E-mail: plant@lambiotte.comWeb site: www.lambiotte.com

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