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Tabel 5-2 Konsep Emulsi Kuantitatif [7, 12]

CTFA/INCI-Names L S Eapp Eres (Eres-Eapp) Karakteristik

Diisostearyl Dimerate 100.0 1.0 33.6 77.1 43.5


Glyceryl Triisostearate 81.6 4.20 30.1 63.7 33.6
Glyceryl 90.8 13.5 39.4 73.0 33.6
Monolsostearate Sangat fatting; emolien super
Glyceryl Triricinoleate 88.6 11.5 37.3 70.8 33.5 protektif; emoliensi sedang
(Castor oil)
Jojoba Oil 77.5 10.4 32.9 62.0 29.1
Isostearyl Isostearate 73.5 6.9 29.2 58.1 28.9
Isostearic Acid 100.0 36.9 58.4 85.5 27.1
Octyl Stearate 80.3 18.1 39.0 65.9 26.9
Propylene Glycol 69.3 13.5 32.2 56.4 24.2
Diisostearate
Propylene Glycol 70.4 16.9 34.9 58.1 23.2
Monolsostearate
Glyceryl Triundecanoate 81.1 27.7 45.8 68.8 23.0
Glyceryl Tricaprylate 70.4 25.8 40.9 60.1 19.2 Fatting sedang; emolien super
Glyceryl 70.9 27.3 42.1 60.8 17.6 protektif dengan emoliensi
Tricaproate/Tricaprate sedang
Octyl Palmitate 59.8 20.8 34.0 50.8 16.8
Glyceryl 69.0 34.6 46.4 61.1 14.7
Tricaprylate/Tricaprate
Squalane 40.0 8.1 18.8 32.6 13.8
Glyceryl 56.1 26.9 36.9 49.4 12.5
Tricaprylate/Tricaprate
Glyceryl 70.3 51.2 58.1 65.9 7.8 Efek pelindung dengan nuansa
Triisononanoate kering
Isopropyl Palmitate 65.6 49.2 55.2 61.8 6.6 Kering merasa; emoliensi yang
kaya
Glyceryl 42.4 31.2 35.2 39.8 4.6 Emolien kering dengan
Triisoundecanoate emoliensi sedang
Glyceryl Trioctanoate 51.6 40.0 44.3 48.9 4.6 Emolien kering dengan
emoliensi yang kaya
Octyl Isostearate 25.6 17.7 20.5 23.8 3.3 Emolien kering dengan
emoliensi yang buruk
Glyceryl Tricaproate 42.6 37.7 39.7 41.5 1.7 Emoliensi sedang
Isostearyl Alcohol 23.6 20.4 21.7 22.9 1.2 Kering, tanpa perlindungan;
buruknya emoliensi
Isopropyl Isostearate 51.0 48.5 49.8 50.4 0.6 Pelindung; merasa kering;
emoliensi yang kaya
Mineral Oil (130 mPas) 10.8 9.6 10.1 10.5 0.4 Kering, tanpa perlindungan;
buruknya emoliensi
Decyl Oleate 26.8 25.4 26.1 26.5 0.4 Kering, tanpa perlindungan;
buruknya emoliensi
Glyceryl 58.8 60.0 60.2 59.1 -1.1 Pelindung; merasa kering;
Tricaproate/Tricaprylate emoliensi yang kaya
Synthetic Squalane 24.9 26.9 26.5 25.4 -1.1 Emolien kering; buruknya
(Polyisobutylene) emoliensi
Diisopropyl Dimerate 69.0 72.3 72.0 69.8 -2.2 Pelindung; merasa kering;
Emolien dari 80 tahun
Dimethicone (350 mPas) 30.1 96.1 75.1 45.3 -29.8 Emulsi adstringen
Isopropyl Myristate 1.0 91.5 62.0 21.2 -40.8 Emulsi adstringen
Est Cw-rel corresponds to the lowest lubricity (L = 0) and the lowest Cw-rel corresponds to
the highest lubricity (L = 100). The second parameter necessary to quantitatively describe
emolliency is the spreading of the emollient on the skin. As the human skin is too variable to
get reproducible results, Roehl, Brand and Withell [7] used gelatin on polyester plates as a
skin substitute for the determination of spreading factors which were calculated from the
contact amgles of emollient droplets on the gelatin surface. For a series of emollients, a scale
of relative spreadability (S) ranging from 0 to 100 was defined, where S = 0 was the
emollient with the lowest spreadability, where as S = 100 was the product with highest
spreadability. Brand [12] presented a Quantitative Emolliency Concept (Table 5-2).

By linear combination of the data obtained from the sensorial judgement of emollients (Fig.
5-1), the relative lubricity (L) and the spreadability (S) Brand calculated the Emolliency of
applications (Eapp) and the residual Emolliency (Eres); The values of >> Eres – Eapp <<,
allows the classification of emollients into several product categories.

 Fatting emollients: high values of Eres and (Eres - Eapp)


 Protective emollients: high values of Eres but low values of Eapp, e.g Eres > 40 = All-
purpose protectivity; Eres > 55-60 = Super protectivity
 Dry emollients: Eres-Eapp = small, i.e. -10 < {Eres-Eapp} < 10. These emollients do not
offer much protection to the skin
 Adstringent emollients: {Eres-Eapp} = < -10 ; they enable the cosmetic chemist to
reduce the oiliness and greasiness of resident emollients, e.g. Isopropyl Myristate reduces
the oiliness and greasiness of vegetable triglycerides such as Avocado Oil, Corn Oil, etc.
The values for Eapp and Eres for mixtures of emollients can easily be calculated on the
basis of the additivity.

In Table 5-2, Isostearic acid and Diisostearyl Dimerate (Diisostearyl Dilinoleate) have the
lowest friction factor, IPM the highest. The liquid isostearic acid is an excellent emollient,
leaving a velvety feel on skin, without being greasy. An improvement of the texture of soap
based emulsions can be obtained by a replacement of a fraction of the stearic acid. With Ca,
Mg or Al neutralized isostearic acid is an excellent stabilizer for W/O emulsions [13].

The synthetic Octyl Stearate is a substitute of Almond Oil, Avocado Oil, Triisostearin, etc. It
should also be noted that Squalane has very different lubricity than Mineral Oil.

5.3.5.1 Spreading Characteristics of Emollients

According to Zeidler [14, 15, 16, 17], emollients can also be characterized by spreading
values (Table 5-3). These have been determined by spreading esters or Guerbet alcohols on
skin and measuring the covered area (in mm2) 10 minutes later. The spreading values of
emollients depend on their chemical structure, consistency and molecular weight. The
spreading values provide information about the fatty character of an emollient which play a
dominant role in the assesment of emollients, e.g. for body lotions or oils which must spread
and absorb easily, the high to medium spreading, low-fatting emollients should be chosen; for
eye care preparations the low-spreading, high fatting emollients are most suitable.
The spreading values are not absolute but relative values and allow the comparison of the
spreading behavior of different emollients on skin. They inform us about how regularly an oil
spreads on the irregular skin surface and how it penetrates and disappears from the surface of
the skin.

5.3.5.2 The Tactile Properties of Emollients

The acceptance of oil preparations by the consumer depends to a large extent on their tactile
properties, i.e. the subjective perception of the product on application. Zeidler [5] made an
attempt to correlate the subjective perceptions, i.e. tackiness and greasiness with physico-
chemical properties such as viscosity and surface tension (Table 5-4). A panel were asked the
following questions: weakly, moderately or strongly greasy or sticky?

Table 5-4 shows the objectively determined tackiness, viscosity, surface tension and the
subjectively evaluated greasiness of some common solvents.

Greasiness is the resistance towards rubbing into the skin; the greasiness as it was perceived
by the panel did correlate with the measured viscosities of the emollients. The sensation of
the tackiness (stickiness) was difficult to evaluate by a panel. A graduated scale of tackiness
could be obtained with a special tensile test arrangement. It was found that tackiness did
correlate both with the viscosity and the surface tension of the emollients tested.

Tabel 5-3 Karakteristik Penyebaran Emolien [2, 10, 14, 15, 16, 17]

INCI-NAMES Nama Dagang Spread Val. CI. PI. Mol. Wt Sifat berminyak dan umum
mm2/10 C digunakan
min.
(1) (6) (7) (8)
Mineral Oil Vaselin Oil 50 Sedikit menyebar; sangat
Peanut Oil Arachid Oil 62 fatting; untuk preparasi
mata, persiapan anti kerut
Almond Oil Sweet Almond 195
dan hiasan. Untuk krim
Oil
pelindung profesional atau
Mineral Oil Paraffin Oil 203
olahraga
(viscous)
Oleyl Erucate Cetiol J 600 (2) 350 < 20 590 Pengganti Jojoba;
penyebaran rendah
Oleyl Oleste Cetiol (2) 450 < 15 530 Sangat fatting; penyebaran
rendah
Caprylic/Capric Myritol 318 (2) 550 < -5 500 Sangat fatting; pelarut yang
Triglyceride baik untuk bahan larut lipid
Octyl Dodecanol Eutanol G (2) 600 < -20 300 Stabil terhadap hidrolisis;
universitas yang berlaku;
sifat penyebaran yang baik
Squalane Squalane; 600 - 422 Afinitas kulit yang tinggi;
Fitoderm (3) sentuhan kulit yang
menyenangkan
Mineral Oil Paraffin Oil, 663 - -
Fluid
Cetearyl Cetiol SN (2) 700 < 15 390 Sedang menyebar; sangat
Isononanoate hidropobik
Oleyl Alcohol HD-Eutanol (2) 700 - Sifat pelarutan yang baik
untuk lipid dan pewarna
yang larut dalam lemak
Isocetylalcohol Eutanol G 16 (2) 700 < -30 250 Sama seperti Eutanol G
tetapi kurang
menggemukkan
Decil Oleate Cetiol V (2) 700 <5 415 Sifat slip yang bagus
Octyl Stearate Cetiol 868 (2) 800 < 10 390 Univ. Aplikasi; penyebaran
sedang
Propylene Glycol Myritol PC (2) 800 < -20 340 Minyak polar sedikit
Dicaprylate/Dicaprate kental, sedikit mengilap;
penyebaran sedang
Dioctylcyclohexane Cetiol S (2) 800 <0 305 Stabil terhadap hidrolisis;
menembus dengan mudah
Coco- Cetiol LC (2) 800 < 15 335 Sifat slip yang baik, sedikit
Caprylate/Caprate menggemukkan
Octyl Palmitate Cegesoft C 24 (2) 900 Max. 2 365 Emolien dengan sifat
Ceraphyl 368 (4) penyebaran yang ditandai
Isopropyl Stearate Isopropyl 1000 < 19 310 Karakter rendah lemak;
Stearate (IPS) (2) penyebaran tinggi
Di-n-Butyladipate Cetiol B (2) 1000 < -25 260 Lemak lemah, menyebar
tinggi, terasa kering
Isopropyl Palmitate Isopropyl 1000 < 15 300 Sifat pelarutan yang baik
Palmitate (2) untuk bahan larut lemak
Crodamol IPP (5)
Hexyl Laurate Cetiol A (2) 1100 < -5 285 Untuk preparat W / O atau
preparat berminyak dengan
kulit kering terasa; daya
pembubaran tinggi untuk
padatan terlarut lipid
Isopropyl Myristate Isopropyl 1200 <2 270 Karakter rendah lemak,
Myristate (2) penyebaran tinggi, sifat
pelarutan yang baik
Dicapryl Ether Cetiol Oe (2) 1600 < -5 240 Stabil terhadap hidrolisis;
sedikit fatting; kulit kering
terasa

Legend :

(1) International Nomenclature Cosmetic Ingredient-Names of the Cosmetic, Toiletry,


and Fragrance Association (CTFA) of the U.S.A
(2) Henkel-Cospha brochures: Cospha products A to Z and “Skin Care Emollients”
(3) Hispano Quimica s.a.;
(4) ISP/Van Dyk;
(5) Croda;
(6) Spreading Val. : Spreading Values, determined according to [14]
(7) Cl. Pt. : Cloud Point determined according to DIN ISO 30 15.
(8) Mol. Wt. : Molecular Weight. The viscosity and stability of a W/O cream correlate
with the viscosity and the Mol. Wt. of the emollient [10].

5.3.6 Emollients for Sunscreen Formulations

Emollients represent the most important emulsion components. Besides the emolliency
which they provide to skin, their solvent power towards certain solid, lipid soluble
sunscreen agents for instance: (INCI-Names) Butyl Methoxydibenzoylmethane, 3(4)-
Methylbenzylidene Camphor, Benzophenone-3, Octyl Triazone etc., are to be taken into
consideration.

According to the FDA Review Panel on OTC Sunscreen Drug Products [21], the
requirements towards an emollient for emulsified sunscreen formulations can be
summarized as follows:

 Stable at pH 4 to 8 and temperatures up to 80°C


 Hydrolysis stable
 Not too greasy, imparting a dry lubricating feel
 Possesses emollient characteristics, i.e. non-drying; forms a protective barrier
 Preferably acts as moisturizer by occlusion
 Should not have degreasing properties
 Absence of an irritant or photo-irritant potential
 Practically odorless and colorless
 Efficient on all types skin
 Easily emulsifiable
 Should not have a destabilizing effect on O/W or W/O emulsions
 Good compatibilty with commonly used cosmetic ingredients
 Good solubility characteristics towards oil- and fat-soluble molecules
 Should not have a negative influence on the ultraviolet absorption curve
 SPF booster

Tabel 5-4 Properti yang Ditentukan Secara Objektif dan Subyektif Emolien [5]

Minyak Produk Tackiness obj. Viskositas Tegangan Greasiness subj.,


(tegangan tarik) pada 30°C permukaan Peringkat [skor]
[mN/cm] [mPa.s] [mN/m]
Hexyl laurate 0.84 ± 0.01 4 31.1 1.5
Isopropyl myristate 0.84 ± 0.02 4 29.1 1.5
Fatty acid cocoalkyl ester 0.86 ± 0.02 8 30.9 3
Paraffin oil, low-viscosity 0.86 ± 0.01 22 30.9 6.5
Octyl dodecanol 0.87 ± 0.01 38 31.2 6.5
Decyl oleate 0.88 ± 0.02 12 32.2 5
Oleyl oleate 0.93 ± 0.01 22 33.2 4
Almond oil 0.94 ± 0.03 49 34.5 8
Paraffin oil, viscous 0.95 ± 0.03 107 32.8 9
Petrolatum 5.81 ± 0.07 Gel - 10

5.3.7 Branched Chain Esters

Table 5-5 shows examples of commercial branched chains esters together with their
properties. Due to their good spreading characteristics [20] and independence of viscosity
from temperature, the saturated branched chain esters have gained in interest. Both the
saturated and unsaturated fatty acids from sebum contain high proportions of branched chain
fatty acids [18]. Sebum, however, is a highly unstable material prone to discoloration and
forming malodorous decomposition products through autoxidatio. Synthetic, stable, saturated
branched chain esters are therefore good substitution products for natural skin lipids.

Weitzel [19] has shown, that the preen gland oil of water-fowl (ducks, gees,swans, seagulls,
pelicans, etc.) chiefly contains branched-chain fatty acid esters. The viscosity and spreading
power of these oils depend very little on temperature and they have a relatively low
solidification point.

Tabel 5-5 Ester Rantai Bermerek

CTFA/INCI-Names Nama Komersial Karakteristik


Cetyl Octanoate Bernel Ester CO (2) Emolien Non Komedogenik
Diisopropyl Dimerate Bernel Ester DID (2) Emolien, Film forner
Diisostearyl Malate Bernel Ester DISM (2) Visco tinggi; untuk sistem anhidrat
Dioctyl Maleate Bernel Ester DOM (2) Larutan non-komedogenik Benzo-3
Octyl Palmitate Bernel Ester EHP (2) Biaya emolien efektif; sangat kering,
Ceraphyl 368 (3) perasaan halus, Pelarut untuk filter UV
Octyl Pelargonate Bernel Ester OPG (2) Emolien kering, tidak berminyak
Trioctyl Citrate Bernel Ester TOC (2) Sebagian menyebar, Emollient Non
Comedogenic
Isocetyl Octanoate Bernel Ester 168 (2) Rasa sutra kering
Octyl Dodecyl Myristate Bernel Ester 2014 (2) Emollient yang kaya, komponen lipstick
Maleated Soybean Oil Ceraphyl CA-D (3) Memperbaharui fungsi penghalang kulit;
pelembap pelembut kulit
Cetyl Lactate Ceraphyl 28 (3) Emolien untuk colognes dan lotion setelah
mencukur
Lauryl Lactate Ceraphyl 31 (3) Pelumas efek dalam emulsi
Alcohols C12-C15 Lactate Ceraphyl 41 (3) Emolien untuk larutan hidroalkohol
Dioctyl Malate Ceraphyl 45 (3)
Tridecyl Neopentanoate Ceraphyl 55 (3)
Isodecyl Oleate Ceraphyl 140-A (3) Ringan, kering, emolien; zat pelarut dan
pendispersi untuk pigmen
Diisopropyl Adipate Ceraphyl 230 (3) Emolien sangat kering yang mengurangi
minyak mineral berminyak; untuk
solubilisasi parfum
Isostearyl Neopentanoate Ceraphyl 375 (3) Membekukan/mencairkan stabilizer,
Dermol 185 (2) pengikat pigmen
Crodamol ISNP (4) Dispersant Carboner; untuk produk
contemplasi mata; penyebaran rendah
Isocetyl Stearate Ceraphyl 494 (3) Sedikit menyebar, emolien kering untuk
Standarnul 7061 (5) krim dan lotion
Isocetyl Stearoyl Stearate Ceraphyl 791 (3) Emolien, pigmen pengikat
Hetester HSS (1)
Octyl Dodecyl-Stearoyl Stearate Ceraphyl 847 (3) Kaya rasa
Triisocetyl Citrate Citmol 316 (2) Penggantian minyak jarak non
komedogenik; bagian spr
Triisoarachidyl Citrate Citmol 320 (2) Pengganti minyak kastor Non
Komedogenik yang sangat kental
Cetearyl Octanoate Crodamol CAP (4)
Purcellin Oil 2/066210 (6)
Isodecyl Neopentanoate Dermol 105 (2) Sedikit menyebar, emolien kering, SPF
Booster
2-Ethylhexyl-2-Ethyl Hexanoate Dragoxat EH (6)
Isoarachidyl Neopentanoate Elefac I-205 (2) Emolien kering; SPF Booster
C12-C15-Alcohols Octanoate Hetester FAO (1) Sangat menyebarkan emolien
PPG-3 Hydrogenated Castor Oil Hetester HCP (1) Secara parsial menyebarkan emolien
Isostearyl Stearoyl Stearate Hetester ISS (1) Sangat menyebar, emollient non
comedogenic
Stearyl stearoyl Stearate Hetester SSS (2) Emolien padat; komponen stick
Propylene Glycol Myristyl Hetester PMA (2) SPF Booster dan solubilizer UV filter;
Ether Acetate penggantian alkohol lanolin asetilated

Tabel 5-5 Ester Rantai Bermerek – Kelanjutan

Stearyl Stearate Hetester 412 (2) Emollient, komponen stick


Triisocetyl Citrate Hetester TICC (1) Secara parsial menyebarkan
emolien
Isocetyl Isostearate -
Octyldodecyl Neodecanoate Neodecanoate-20 (10)
Isopr. PPG-2 Isodeceth-7 Velsan D8P-3 (9) HLB 14; emollient co-emulsifier,
Carboxylate sol. Benzo-3
Isopr. C12-15 Pareth-9 Velsan P 8-3 (9) HLB 18; larut dalam air; emolien
Carboxylate untuk produksi mandi
Isononyl Isononanoate Wickenol 151 (7)
Isodecyl Isononanoate Wickenol 152 (7)
Isotridecyl Isononanoate Wickenol 153 (7)
Isostearyl Isostearate Wickenol 133 (7)
Prisorine 2039 (8)
Suppliers

(1) Heterene; (2) Bernel/Alzo; (3) ISP/Van Dyk (4) Croda; (5) Henkel; (6) Dragoco; (7) Wickhen; (8)Unichema;
(9)Sandoz; (10) Nikkol

5.3.8 Other Emollients

Lanolin: according to the Pharmacopea Helvetica V (Ph.H.V), it has the compotition: Adeps
lanane/olive oil/water 70:10:20 or according to Deutsches Arzneibuch VIII (DAB 8): Adeps
lanae/paraffin oil/water 65:15:20. Lanolin is an absorption base (see chapter 8) that can be
absorb up to 300% of its weight of water or aqueous solutions containing active ingredients:
it forms a lipid emollient film which is beneficial in the case of inflammations. Lanolin has a
mild bacteriostatic effect and promotes wound healing. In the past, cases of eczematous
hypersensitivy towards wool wax based cosmetics preparations have been recorded.
Nowadays, more skin-friendly, purified lanolin and lanolin oil type products are available on
the market [2]. One lanolin substitute is, for instance: Glyceryl/Sorbitol
Oleate/Hydroxystearate (and) Paraffin (INCI-Name) [34].

Jojoba Oil: the jojoba-plant Simmondsia chinensis (Buxaceae) is a man-high shrub,


discovered for the first time in the dessert of Baja California (Mexico). This plant thrives at
elevated environtmental temperatures, low humidities and in soils with high salinity or
marginal fertility. The olive-like fruit contain 45-55% of a liquid wax (not a triglyceride)
consisting of monoesters between Δ-9 cis-monounsaturated linear fatty alcohols and Δ-9
linear fatty acids. In a typical analysis of the wax esters contained in jojoba oil, the following
major alcohol/acid combinations have been found [22]:

37% C22/C20, 24.3% C20/C20, 10.5% C20/C22, 7% C24/C20

5.4% C20/C18, 3.6% C22/C18, 2.1% C22/C22, etc.

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