Journal of Oleo Science

Copyright ©2021 by Japan Oil Chemists’ Society

J-STAGE Advance Publication date : July 9, 2021
doi : 10.5650/jos.ess21078
J. Oleo Sci.

REVIEW

Performance of Green Surfactants in the

Formulation of Heavy-Duty Laundry Liquid
Detergents (HDLD) with Special Emphasis on Palm
Based Alpha Methyl Ester Sulfonates (α-MES)
Siew Yan Low1, Jen Yen Tan1, Zhen Hong Ban1,2 and Parthiban Siwayanan1,2＊
1
 chool of Energy and Chemical Engineering, Xiamen University Malaysia, Jalan Sunsuria, Bandar Sunsuria, 43900 Sepang, Selangor,
S
MALAYSIA
2
College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, CHINA

Abstract: Liquid detergent has an increasing demand in North America, Western Europe, and Southeast
Asia countries owing to its convenience to use and efficiency to clean. Alpha methyl ester sulfonates (α-
MES), an anionic surfactant derived from palm oil based methyl ester, was reported to have lower
manufacturing cost, good detergency with less dosage, excellent biodegradability, higher tolerance to hard
water, and lower eco-toxicity as compared to linear alkylbenzene sulfonates (LABS). LABS was known as
the workhorse of the detergent industry in the 20th century. Although palm-based α-MES was successfully
used as the sole surfactant in powder detergent, there are still some unsettled technical issues related to
phase stability and viscosity when using this anionic surfactant in heavy-duty laundry liquid detergent
formulations. This paper will review not only the market overview of detergents, the application and
performance of green surfactants in laundry detergents but also will highlight the technical issues related to
the application of palm-based α-MES in laundry liquid detergent and some of the possible methods to
overcome the formulation adversities.

Key words: green surfactants, heavy-duty laundry liquid detergents, palm-based alpha methyl ester sulfonates

1 Introduction convenient to use and does not require measurement of

Laundry detergent, used for cleaning of fabrics, has amount needed for each wash load1）.
many different formats including powder, liquid, bar, tablet, Heavy-duty laundry detergent, commonly available in
and sachet to suit consumers’preferences. Powder deter- powder and liquid form, is capable of removing deposition
gent was favoured in Asia countries including China, India, of heavy soil from textiles through washing process3）.
and Japan, owing to its low cost per wash load and high Heavy-duty laundry detergent generally has higher con-
volume over weight ratio1）. Liquid detergent is very popular centration as compared to light-duty laundry detergent,
in North America and Western Europe as it is effective in therefore it is commonly used in washing machines3）. Table
pre-treating and removing stains, ready for immediate use, 1 and Table 2 show the typical formulations for unbuilt and
have no solubility issues, do not require prewashing, and （HDLD）
built heavy-duty laundry liquid detergent 4）
.
hence is time and energy saving1−3）. Detergent in bar form
was preferred by Indians prior to switching their prefer-
ences into powder detergent as they deemed the rubbing
action is important to effectively clean the fabrics1）. On the 2 Market Overview of Detergents
other hand, detergent in tablet and sachet form was highly The major companies in detergent market include
preferred in United Kingdom and European Union as it is Procter & Gamble, Unilever, Henkel, Lion Corporation, Kao

＊
Correspondence to: Parthiban Siwayanan, School of Energy and Chemical Engineering, Xiamen University Malaysia, Jalan
Sunsuria, Bandar Sunsuria, 43900 Sepang, Selangor, MALAYSIA
E-mail: [email protected]
Accepted April 7, 2021 (received for review March 2, 2021)
Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online
http://www.jstage.jst.go.jp/browse/jos/  http://mc.manusriptcentral.com/jjocs

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 S. Y. Low, J. Y. Tan, Z. H. Ban et al.

Table 1　Typical Formulation for Unbuilt

HDLD4）.
Components Weight (%)
Nonionic surfactant 20-40
Anionic surfactant 10-30
Triethanolamine 0-8
Ethanol 0-7
Fluorescent whitening agent 0.2-0.4
Perfume 0.05-0.1
Dye q.s.
Water to 100
Fig. 1　Global market share of laundry detergent by region
Table 2　Typical Formulation for Built HDLD4）. in year 20167）.
Components Weight (%) cluding China, India, and Brazil as the consumers in these
Nonionic surfactant and/or anionic countries would prefer economical products7）. There is also
5-15
surfactant a large percentage of population based in rural areas that
Builder 20-30 would prefer powder detergent than other products7）.
Liquid detergent is likely to have a higher growth rate as
Sodium silicate 2-5
compared to powder detergent due to large-scale adoption
Polymeric stabilizers 0-2 in North America and Western Europe countries7）. Liquid
Sodium xylene sulfonate 0-5 detergent is more convenient and comfortable to use as
Emulsifying agents 0-2 compared to powder detergent7）. The market growth of
liquid detergent in Asia Pacific, North America, and Europe
Sodium carboxymethylcellulose 0-2
are expected to be 5.9％, 4.6％, and 4.5％ respectively
Fluorescent whitening agent 0.2-0.4 during year 2019 to 20255, 8, 9）.
Perfume 0.05-0.1 Detergent in tablet form is likely to observe slow growth
Dye q.s. and decreasing trend in market share by year 20257）. This
is because tablet detergent is less popular as compared to
Water to 100
rising demand of liquid products in developed economies
and great penetration of powder products in developing
Corporation, Church & Dwight, Johnson and Son, Colgate- countries7）.
Palmolive, and Amway Corporation1, 5）.
2.2 Asia Pacific
2.1 Global The laundry detergent market in Asia Pacific had
In year 2016, the demand for laundry detergent market achieved USD 34.5 billion in year 2019, which had signifi-
had reached USD 133.3 billion globally and it was antici- cant contribution in the growth of the global laundry deter-
pated for a compound annual growth rate（CAGR） of about gent market 10）. China, being the major market in Asia
4.9％ from year 2017 to 2025, and to exceed a total Pacific, accounted for about 70％ of the contribution10）. In
revenue of USD 205.2 billion by year 20256）. Among all coming few years, India is expected to grow more rapidly
products, powder detergent had the biggest market share, as compared to China10）. Hence, China and India are the
accounting for more than 31％ of the total revenue in year market leaders that have major effect on Asia Pacific
20166）. Among all applications, household application oc- laundry detergent market with their rising demand10）. De-
cupied the largest share with an expected demand of over tergent in powder form is leading in Asia Pacific region
USD 118 billion by year 2025, growing at a CAGR of 4.9％6）. with expected robust growth of liquid detergent in coming
Figure 1 shows the global market share of laundry deter- years due to its convenience and ease to use10）. The driving
gent by region in year 2016. It can be observed that Asia forces of Asia Pacific laundry detergent market include
Pacific market had occupied the largest share, followed by rapid urbanization and changing lifestyles of people,
Europe and North America7）. growing in both middle-class population and their dispos-
Powder detergent is expected to dominate the market able incomes, growing public awareness on health and
over year 2018 to 2025 and it is expected to have strong hygiene, and growth of tourism and hospitality indus-
growth and steady penetration in developing countries in- tries10）.
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 Performance of Green Surfactants in the Formulation of Heavy-Duty Laundry Liquid Detergents (HDLD)

2.3 Southeast Asia

The laundry detergent market in Southeast Asia will be
discussed focusing on four countries which include Malay- Fig. 2　Chemical structure of FAS22）.
sia, Singapore, Thailand, and Vietnam. In Malaysia, rising
demand of liquid laundry detergent can be observed espe-
cially in urban areas where people prefer convenient and
efficient products. Consumers in rural areas are being Fig. 3　Chemical structure of FAE24）.
gradually influenced as well owing to the increasing variet-
ies and advertisements on liquid laundry detergent11）. In
Singapore, consumers tend to opt for quality over quantity
Fig. 4　Chemical structure of FAES25）.
in recent years, leading to increasing attention in premium
laundry detergent12）. In year 2018, a new liquid tablet de-
tergent hit the Singapore market because of its conve- 3.2 Oleo-based fatty alcohol ethoxylates（FAE）
nience to use as no measurement of detergent was re- Oleo-based fatty alcohol ethoxylates（FAE）are non-ionic
quired12）. In Thailand, liquid detergent with scent booster surfactant produced from the reaction of fatty alcohol and
has increasing demand due to the tropical and humid ethylene oxide with the presence of alkaline catalysts23）.
climate that result in perspiration and unpleasant odour on FAE are commonly used as foaming agent in personal care,
clothing13）. In Vietnam, the laundry detergent market has wetting agent in detergent, and surfactant in household
seen rising demand in concentrated liquid detergent and and industrial products23）. Figure 3 shows the chemical
liquid fabric softener as the consumers were slowly switch- structure of FAE.
ing from concentrated powder detergent14）.
3.3 Oleo-based fatty alcohol ether sulfates （FAES）
Oleo-based fatty alcohol ether sulfates（FAES）are pro-
duced with addition of ethylene oxide to fatty alcohol, fol-
3 Overview of Green Surfactants lowed by sulphation of fatty alcohol ethoxylates, then neu-
Surfactant, the main component in formulation of deter- tralized using different alkaline25）. FAES are highly water
gent, has high environmental relevance due to large pro- soluble, less sensitive to hard water, more stable in alkaline
duction volume and its discharge into the environment environment, have good rheological behaviour, good foam-
either after treatment or without treatment 15）. For in- ability, and better skin compatibility21, 22）. They have wide
stance, LABS, the workhorse in detergent industry derived application in heavy-duty and light-duty detergents, per-
from petrochemical feedstock, and phosphate-based build- sonal care products, and industrial cleaners22）. Owing to
ers used in detergent formulation, have harmful effects on their low skin irritation property, FAES are suitable to be
the environment 1）. As consumer awareness arises, the used in formulation of baby products20）. Figure 4 shows the
demand towards development of renewable and green sur- chemical structure of FAES.
factants without incorporation of phosphate-based builders
increases16, 17）. Green surfactants can be either oleochemi- 3.4 Oleo-based methyl ester ethoxylates （MEE）
cal based surfactants or microbial based biosurfactants Oleo-based methyl ester ethoxylates （MEE）are non-ionic
where some of the commonly used green surfactants are surfactant produced from the reaction of methyl ester and
discussed in detail18）. ethylene oxide under calcium or magnesium based cata-
lysts26）. The properties of MEE are similar with FAE except
3.1 Oleo-based fatty alcohol sulfates （FAS） for having lower foaming power and being less skin irritat-
Oleo-based fatty alcohol sulfates（FAS）are anionic sur- ing27）. MEE are common alternative detergent product to
factant produced from sulphation of fatty alcohol with FAE owing to their lower cost26）. However, the poor hydro-
chain length of C8 to C20, followed by neutralization to form lytic stability of MEE in alkaline environment and lack of
stable salt, commonly sodium, potassium, ammonium, or gel phase limit their application in some powder and liquid
magnesium salt, and lastly drying19）. FAS have excellent detergent formulations26）. The lack of gel phase was due to
foaming and cleansing properties20）. C 10 to C 18 FAS are terminal methoxy group in MEE that reduces their hydro-
commonly used in many formulations of personal care and gen bonding and subsequently reduces their solubility in
laundry washing with addition of other surfactants to water and their tendency to form aqueous gels28）. Despite
enhance their properties21）. FAS have limited solubility and that, MEE may be useful in reducing the gelling of aqueous
hence are used in formulation of cream and paste shampoo, solution in formulation of liquid products28）. Figure 5 shows
toothpaste, and cosmetics cream 21）. Figure 2 shows the the chemical structure of MEE.
chemical structure of FAS.

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J. Oleo Sci.
 S. Y. Low, J. Y. Tan, Z. H. Ban et al.

Table 3　Krafft points of some surfactants.

Surfactant Krafft Point (℃) Reference
LABS (C14/C16) 8/13 Dobson et al.39)
α-MES (C14/C16) 10.1/24.8 Yavrukova et al.38)
FAS (C14/C16/C18) 26/36/56 Zelmer40)

Fig. 5　Chemical structure of MEE29）. plantarii33−35）. Rhamnolipids are widely used in various in-
dustries such as detergents and cleaners, bioremediation
and enhanced oil recovery, pharmaceuticals and therapeu-
tics, cosmetics, and agriculture industry35）. For instance,
TeeGene BioTech, AGAE Technologies LLC, and Jeneil
Biosurfactant Co. LLC have included rhamnolipids in their
formulation in producing variety of products35）.

Fig. 6　Chemical structure of α-MES22）.

3.5 Oleo-based methyl ester sulfonates （MES） 4 M ES and Its Performance in Liquid Detergent
Oleo-based alpha methyl ester sulfonates（α-MES）are Formulation
anionic surfactant mainly derived from palm oil based The performance of surfactants in liquid detergent for-
methyl ester30）. The manufacturing process of α-MES is mulation can be determined by looking at the following
relatively simple and requires lower manufacturing cost as properties which include solubility, viscosity, phase stabili-
compared to LABS, the workhorse of detergent industry ty, tolerance in hard water, detergency, wettability, foaming
which are derived from petrochemicals30）. Due to the inex- ability, biodegradability, and eco-toxicity. Emphasis will be
pensive feedstock of α-MES, the cost of a α-MES plant given on the performance of α-MES as compared to LABS,
would be only around one fifth of that required to produce the workhorse of detergent industry.
LABS on an equal capacity basis30）. α-MES have several ad-
vantages as compared to LABS which include greater de- 4.1 Solubility
tergency with less dosage, greater biodegradability, higher The solubility of surfactants depends on their individual
tolerance to hard water, lower toxicity to environment, Krafft point. Krafft point is the temperature where the sol-
better skin compatibility, and good return on investment ubility of an ionic surfactant is equal to its critical micelle
owing to the low manufacturing cost30−32）. Figure 6 shows concentration（CMC） 37）
. At temperature below Krafft point,
the chemical structure of α-MES. surfactants will form precipitates instead of micelle, which
result in less effective performance of surfactants in clean-
3.6 Sophorolipids ing37）. The Krafft points of α-MES surfactants are in the
Sophorolipids are one of the nonionic glycolipid surfac- range of 10.1℃ to 24.8℃ depending on their carbon chain
tants, produced by non-pathogenic yeast such as Candida length while it is 65℃ for their di-salt37, 38）. Therefore, with
bogoriensis, Candida bombicola, and Candida higher Krafft point and presence of large amount of di-salt,
apicola33）. Sophorolipids can be widely applied in various significant amount of precipitates will form and reduce the
industries such as cosmetics, food, cleaning, and petroleum solubility of surfactant, result in poorer quality of α-MES37）.
industry34）. For instance, Ecover Belgium, MG Intobio Co. In Table 3, the Krafft points of some surfactants were
Ltd, and Synthezyme LLC have included sophorolipids as listed. It can be observed that although the Krafft point of
surfactant in some of their formulation in hard surface α-MES is higher than LABS, their Krafft point is still lower
cleaners, laundry detergents, and soaps35）. Saraya Co. Ltd, as compared to FAS. Hence, α-MES surfactants are less
a Japanese company, has also commercialized sophoron, soluble than LABS but are more soluble than FAS.
which is a dish washing detergent formulated with sopho-
rolipids as surfactant33）. Sophorolipids are found to possess 4.2 Viscosity
antimicrobial, antifungal, and anticancer properties as Viscosity, defined as the resistance against deformation
well36）. for a fluid, varies between different fluid41）. Viscosity is
used to measure the thickness of a fluid to make sure it is
3.7 Rhamnolipids not too thick to pour nor too thin to appear watery42）. Vis-
Rhamnolipids are another nonionic glycolipid surfac- cosity can be measured using rheometer. Detergent within
tants, produced by bacteria such as Pseudomonas aerugi- a certain range of viscosity has more pourable flow without
nosa, Pseudomonas chlororaphis, and Pseudomonas the need to modify the detergent formulation42）. It was re-
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 Performance of Green Surfactants in the Formulation of Heavy-Duty Laundry Liquid Detergents (HDLD)

Table 4　Cloud point of some surfactants. Table 5　Types of soil and fabric used to measure the
detergency of α-MES and LABS18）.
Surfactant Cloud Point (℃) Reference
LABS −3 – 11 Cohen et al.45) Swatches Soil Fabric
α-MES 20 – 26 Cohen et al. 45) JB-01 Mineral oil, carbon black Cotton
MEE 53 – 62 Kolane et al.29) JB-02 Egg yolk Cotton
FAE 78.5 Kolane et al. 29) JB-03 Sebum, pigment Cotton
W20D Sebum, pigment Polyester/Cotton

ported that viscosity build-up issue is very common when W20PF Vegetable oil, pigment Polyester/Cotton
it comes to incorporation of α-MES surfactant in formula-
tion of liquid detergent. mulation are those with low CMC and cloud points. The
cloud point of a detergent is the temperature at which a
4.3 Phase stability detergent solution passes from an isotropic micellar system
Liquid detergent has to be fluid, homogeneous and into a two-phase system. The cloud points of some surfac-
phase-stable across storage conditions. Phase stability is an tants including α-MES are shown in Table 4.
essential criterion in liquid detergent formulation and
therefore phase separation that will result in shorter shelf 4.4 Tolerance in hard water
life must be prevented. In addition, it will also result in Tolerance of surfactants in hard water is evaluated by
poor quality of liquid detergent and negative impact in their ability to tolerate the water hardness ions, which are
consumers’acceptance43）. Phase stability test can be eval- calcium and magnesium ions, commonly present in hard
uated by placing 300 mL of liquid detergent in a 500 mL water. The water hardness ions might cause precipitation
plastic jar with sealed cap for at least 48 hours at 5℃, 25℃, of surfactants and hence affect their performance46）. Sur-
and 40℃ respectively under atmospheric pressure44）. If the factants that have higher tolerance and are less sensitive to
liquid detergent did not split into layers or split into layers these water hardness ions generally have better detergency
with major layer consists of at least 95％ of the composi- than the other. Michael Shea 30）stated that α-MES have
tion by weight, then it is considered as phase stable44）. It higher detergency and higher tolerance in hard water as
was reported that phase stability is one of the commonly compared to LABS. Figure 7 shows the detergency of
associated issues with the formulation of α-MES in liquid α-MES and LABS on different types of soil in different
detergent. Generally, hydrotropes are often added to the water hardness in terms of cumulative soil removal index.
liquid detergent composition to prevent phase separation. The types of soil were listed in Table 5 together with the
Surfactants that preferred for use in liquid detergent for- fabric used. It can be easily observed that the detergency

Fig. 7　Detergency of α-MES and LABS on different types of soil in different water hardness18）.
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 S. Y. Low, J. Y. Tan, Z. H. Ban et al.

of α-MES is always better than LABS regardless of the Table 6　Time taken for LABS and α-MES to completely
types of soil and the water hardness. Hence, it was proven immerse into unsoiled cotton swatch at different
that α-MES have higher tolerance in hard water than water hardness45）.
LABS.
Surfactant Water Hardness (ppm) Time Taken (s)

4.5 Detergency 150 7

Detergency of surfactants is defined as their capability LABS 400 228
to remove soil from fabric during cleaning process41）. The 650 300
detergency test for detergent with different formulations
150 300
can be evaluated by the washing of artificially soiled
swatches either through standard top loading washing α-MES 400 300
machine or Terg-O-Tometer43, 47）. The reflectance of original 650 300
unsoiled swatches and the reflectance of swatches before
and after washing were measured using Minolta spectro- 4.7 Foamability
photometer43）. The values were then used to calculate the Foamability, which include foam producing power, foam
detergency of different detergent formulations using Equa- stability, and foam durability, is commonly used to charac-
tion 1. terize stable foams41）. Foamability is a measure of foam
AW−BW volume immediately after the generation of foam, while
Detergency＝［ ］ ×100 （1）
OC−BW foam stability is a measure of the lifetime of the foam41）.
where AW is the reflectance of swatches after washing, BW The foamability test can be conducted by filling 200 mL of
is the reflectance of swatches before washing, and OC is 0.1％ detergent solution into a 500 mL measuring cylinder
the reflectance of original swatches before soiling43）. Re- and perform constant rate stirring for 30 times using a
searches shown that α-MES have better detergency than glass rod with perforated base to generate foam43）. The
LABS and require less concentration of surfactant to initial volume of foam generated was recorded as the foam-
achieve comparable detergency 48）. The detergency of ability of detergent solution43）. After 5 minutes, the final
α-MES and LABS in terms of cumulative soil removal index volume of foam was recorded and the rate of decay is the
can also be observed in Fig. 7. By looking at the value of foam stability43）. Table 7 shows the initial foam height at t
cumulative soil removal index, it was proven that no matter ＝0 min and the foam height at t＝5 min of α-MES and
at which level of water hardness, the detergency of α-MES LABS, measured in mm. It can be observed that the foam-
is always better than LABS regardless of the types of soil. ability of α-MES is weaker but comparable with the foam-
ability of LABS.
4.6 Wettability
Wettability is the degree of wetting to measure the 4.8 Biodegradability
ability of a liquid to spread on a solid surface or on another Biodegradation is a process where microorganisms
immiscible liquid 41）. Wetting test can be conducted by undergo series of enzymatic reaction to break down the
dropping a 2 cm×2 cm unsoiled cotton swatch, condi- organic substances into less complex chemicals include
tioned at relative humidity of 20％ for 24 h, using a pair of carbon dioxide, water, and biomass41）. To measure the bio-
tweezers, into the prepared 100 mL round container con- degradability of detergent solution, Closed Bottle Test was
sists of 0.1％ detergent solution and record the time taken carried out following the Organisation for Economic Co-op-
for complete immersion of solution31, 43）. The time taken for eration and Development（OECD） Guidelines41）. In this test,
the unsoiled cotton swatch to have complete immersion in the dissolved oxygen（DO） content of two bottles contained
α-MES and LABS detergent solution at different water certain amount of active sludge, one with and one without
hardness is shown in Table 6. It can be observed that detergent solution, was measured41, 48）. The biodegradation
α-MES takes longer time to completely immerse into the profile was then developed by using the measured DO
unsoiled cotton swatch than LABS, which means the wet- content over a 28-days period at 22-25℃48）. To qualify as
tability of α-MES is weaker than LABS. readily biodegradable, 60％ biodegradation should be
reached within 28 days under aerobic conditions41）. Re-

Table 7　Foam height of α-MES and LABS at t＝0 min and 5 min49）.
Surfactant Foam Height (mm) (t = 0 min) Foam Height (mm) (t = 5 min)
LABS 190 135
α-MES 170 115

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 Performance of Green Surfactants in the Formulation of Heavy-Duty Laundry Liquid Detergents (HDLD)

Table 8　Readily biodegradability of some surfactants under aerobic conditions.

Surfactants Percentage of biodegradation (Duration) Reference
LABS (C10-C13) 70 % (13 days) Ishak et al.50)
100 % (1 day) Swisher51)
FAS
95-98 % (5 days) Steber et al.52)
FAES 96 % (30 days) Felletschin et al.53)
FAE (Linear) > 80 % (28 days) Kravetz et al.54)
FAE (Branched) 40 % (28 days) Kravetz et al.54)
α-MES (C12/C14/C16) > 90 % (8 days/14 days/26 days) Ishak et al.50)

Table 9　L C 50 of LABS and α-MES on of powder detergent has been successfully developed by a
Tilapia nilotica55）. number of researchers. Besides that, palm oil based α-MES
has also been used in the formulation of liquid products
Surfactants LC50 (mg/L), 96 h
such as household cleaning product, personal care,
LAS (C10-C13) 11.4 laundry, and industrial cleaning product.
MES (C14/C16/C18) 22.6/12.6/56.6 In year 2007, a patent was published by World Intellec-
tual Property Organization on the process for manufactur-
searches shown that α-MES have better biodegradability ing liquid detergent containing α-MES56）. The first step is
than LABS as the time required to achieve the 60％ pass to form a liquid detergent partial composition in the first
level is much shorter than LABS48）. The biodegradability of vessel which has a pH of 5 to 956）. The second step is to
some surfactants is listed in Table 8 for comparison adjust the pH to make sure it is in the range of 7 to 956）.
purpose. Then, about 0.5％ to 15％ of α-MES is added with mixing
to form liquid detergent at temperature of about 20℃ to
4.9 Eco-toxicity 60℃56）. The detailed ingredients used in the liquid deter-
Eco-toxicity, also can be referred as aquatic toxicity, is a gent formulation can be found in the patent.
measurement of toxicity of detergent solution when dis- In year 2010, a US patent regarding laundry detergent
charged into aquatic environment41, 43）. Eco-toxicity of de- containing α-MES was published57）. Successful formulation
tergent solution can be determined using Fish Acute Toxic- of liquid laundry detergent with great cleaning perfor-
ity Test, which is also under OECD Guidelines48）. The test mance and stability was developed using α-MES with
was conducted in two stages, the first stage is the range- higher level of di-salt, and the color of α-MES can be
finding test and the second stage is the definitive test48）. In reduced by carrying out a more rigorous bleaching step57）.
the first stage, the fish were exposed to varying concentra- The liquid laundry detergent shall consists of about 6％ to
tion of detergent in logarithmic series for a period of 24 35％ of surfactant, where the ratio of C16 α-MES to total
h48）. The concentration where there is no mortality and surfactant is preferably less than 0.258）. The detailed for-
where there is 100％ mortality was recorded and was uti- mulation can be found in the patent.
lized in the second stage where the fish were exposed to In year 2014, R & D Department from Lion Eco Chemi-
varying concentration of detergent in geometric series and cals Sdn Bhd presented MES Technical Presentation for
the mortalities were recorded respectively at period of 24, Liquid Detergent. It shows that MIZULAN, which is one of
48, 72, and 96 h48）. The concentration of detergent that the α-MES surfactants, has superior detergency as com-
killed 50％ of the fish, labelled as LC50, was determined and pared to LABS and FAS58）. The detergency of α-MES on
the eco-toxicity was rated based on a rating scheme from sebum is excellent compared to AES and LABS under dif-
the U.S. Fish and Wildlife Services48）. Table 9 shows the ferent concentration of surfactant, different water hard-
LC 50 of LABS and α-MES on Tilapia nilotica. It was ness, and different temperature 59）. α-MES have good
proven that α-MES have lower eco-toxicity as the LC50 for enzyme compatibility, anti-soil deposition property, and
α-MES is higher than LAS, which means it requires higher biodegradability58）.
concentration of α-MES to kill 50％ of the fish. In year 2017, Maurad et al.43）had successfully formulated
five palm-based liquid detergents（PBLDs）with clear ap-
pearance, single phase, and pourable viscosities using C16/18
α-MES as surfactant. There are a few important points to
 pplication of Palm Oil Based α-MES in Formulation
5 A take note, where the heat sensitive ingredients including
of Liquid Detergent optical brightener, enzyme, preservative, and fragrance
The application of palm oil based α-MES in formulation should be added in the cooling stage, and the pH of the de-
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J. Oleo Sci.
 S. Y. Low, J. Y. Tan, Z. H. Ban et al.

tergent solution should be maintained below 10 to prevent detergent performance31）.

increase of hydrolysis rate that would affect the stability of
liquid detergent 43）. Study has shown that the PBLDs
possess excellent detergency in removal of oil based stains
and protein based stains, similar foamability and foam sta- 6 T
 echnical Issues Associated with Palm Oil Based
bility, and greater wettability and biodegradability as com- α-MES in Heavy Duty Laundry Liquid Detergent
pared to the commercial liquid detergent43）. （HDLD）Formulation and Possible Methods to
In year 2018, Tai et al.49）had formulated a dishwashing Overcome the Technical Issues with Enhanced
liquid detergent with α-MES surfactant. It was shown that Formulation
the α-MES solution was stable and did not hydrolyse obvi- α-MES was not extensively used in the formulation of
ously at pH range of 4 to 9, while at pH larger than 10, the HDLD due to some of the technical issues regarding phase
hydrolysis occur49）. α-MES and LABS both have good foam stability and viscosity build-up of liquid detergent upon
stability, however the foamability of α-MES is slightly prolonged storage. The technical issues and possible
weaker than LABS, hence it is suitable in application of de- methods to overcome with enhanced formulation are dis-
tergent formulation that requires low foam49）. Study shown cussed in this section.
that α-MES have better calcium soap dispersing power,
greater tolerance in hard water, and better detergency as 6.1 Phase stability
compared to LABS49）. The prepared dishwashing detergent It was reported in some of the researches that phase sta-
using α-MES in this research had been proven to exhibit bility issue of liquid detergent formulated with α-MES sur-
good stability with no phenomenon of flocculation or strati- factant may occur at lower temperature, at higher pH and
fication observed after storing for 6 months49）. upon prolonged storage. This is one of the challenges when
In year 2019, Djohan et al.60）had synthesized α-MES sur- formulating liquid detergent with α-MES surfactant.
factant from purified waste cooking oil and combined with Through years of researches, some possible methods to
ZnO nanoparticles to produce nanofluid detergent. The overcome the phase stability issue with enhanced formula-
stability and detergent performance of the nanofluid deter- tion have been proposed.
gent with constant ZnO concentration of 0.1％ and varying One of the methods is to incorporate appropriate hydro-
α-MES concentration of 10％, 12.5％ and 15％ were dis- trope to the formulation that may display synergism with
cussed60）. The stability test was conducted 24 h after syn- palm based α-MES and is expected to produce a phase
thesis of nanofluid detergent, which shows that nanofluid stable HDLD formulation with acceptable viscosity.
detergent that contains 15％ α-MES concentration has the However, these hydrotropes might be expensive and
highest stability60）. On the other hand, the detergency test require great quantity in some formulations. Hence, the
was also carried out, with and without UV lamp that helps cost effectiveness of the formulation shall also be taken
to activate the nanoparticles to degrade methylene blue60）. into consideration besides studying the synergistic effect
It shown that the nanofluid detergent with 15％ α-MES between α-MES and hydrotope as well as the resulting
concentration has the best performance, with and without performance of liquid detergent.
the presence of UV lamp, among all60）. With the presence Another US patent had suggested the addition of inor-
of UV lamp, the performance for all nanofluid detergents ganic salts, for example formaldehyde-cross-linked hydro-
had improved60）. lyzed polyacrylonitrile into the liquid detergent formulation
In year 2019, Permadani and Slamet31）had also synthe- to improve the phase stability61）.
sized α-MES surfactant from purified waste cooking oil and Morigaki et al.62）had published a patent on methods to
combined with carboxymethyl cellulose and TiO2 nanopar- formulate a phase stable liquid detergent with α-MES. The
ticles to form nanofluid detergent. The detergent stability liquid detergent should contain α-MES, an alkylbenzene
and performance were tested with constant concentration sulfonate, a polyoxyethylene alkyl ether sulfate, and an al-
of TiO2 nanoparticles at 0.1％ and varying concentration of kanolamine62）. Following the mass ratio mentioned in the
α-MES surfactant as well as carboxymethyl cellulose31）. patent, the improved phase stability of liquid detergent
The results show that nanofluid detergent is stable with under low temperature of about −20℃ to room tempera-
the concentration of α-MES above 1.1 wt％31）. The deter- ture was proven62）.
gent performance increases with increase concentration of Lion Eco Chemical Sdn. Bhd. had also proposed another
α-MES surfactant31）. With the presence of mercury lamp enhanced formulation using 15％ α-MES-Na, 5％ alkanol-
that activates TiO2 nanoparticles for stain degradation, the amine, preferably monoethanolamine, and control the pH
performance of nanofluid detergent achieves further im- to 7.5 using sulphuric acid to produce clear and free
provement31）. It shown that with the addition of 4％ car- flowing liquid detergent without phase separation59）. It was
boxymethyl cellulose, the stability of the nanofluid deter- shown that the solubilisation temperature had decreased
gent can be improved while maintaining the optimum from 34℃ to 22℃59）.
8
J. Oleo Sci.
 Performance of Green Surfactants in the Formulation of Heavy-Duty Laundry Liquid Detergents (HDLD)

Regarding the phase stability issue due to higher pH, viscosity modifiers are introduced to the formulation as
Maurad et al.43）and Tai et al.49）had reported that hydrolysis well. Hence, there is huge potential for α-MES to replace
occurred at pH above 10 and it is stable at pH range of 4 to LABS in near future.
9. On the other hand, some ingredients that were sensitive
to the order of addition into the formulation will also con-
tribute to the phase stability issue of formulation. Hence,
Maurad et al.43）suggested to add ingredients that were sen- Acknowledgment
sitive to heat in the cooling stage and to control the pH of This work was funded by Xiamen University Malaysia
the formulation below 10. Research Fund（Grant no. XMUMRF/2019-C3/IENG/0012）.

6.2 Viscosity
Viscosity build-up issue was reported in some studies
when it comes to formulation of liquid detergent with References
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11
J. Oleo Sci.