555674999-Soap-and-Detergent-Manufacturing-Course-2nd-Sem-2019.pdf

AN-NAJAH NATIONAL UNIVERSITY
FACULTY OF ENGINEERING AND INFORMATION
TECHNOLOGY
DEPARTMENT OF CHEMICAL ENGINEERING
Soap and Detergent Manufacturing (64475 or 10626475)
Designed by: Prof. Amer M. EL-Hamouz
Instructor: Majd Shhadi, PhD
Second Semester 2019/2020

Office: Room # 1300, Engineering Building (11)
email: elhamouz@najah.edu
Office Hours: Hours posted on door

THIS COURSE
 This is an industry related course.
 Students can learn more on how to manufacture soap and detergents.
 The course will also equip students with the chemistry behind soap,
detergent and cosmetic emulsion manufacturing.
 Students will learn more about surfactants used in manufacturing soap
and detergents. Household cleaning and disinfection products will be
discussed in this course.
• The last topic to be discussed in this course is the mixing roles in soap
and detergent manufacturing. All safety issues related to soap and
detergent manufacturing steps will be covered.
• During the course, students will be asked to make visits to local chemical
industry.
• Several assignments will be based on such visits. Students will apply
what they learn in this course by carrying out experiments in the
department’s lab
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Objectives
By the end of this course, you will be:
 Able to understand the fundamental theories, practical applications, and
manufacturing aspects of liquid detergents, from light duty liquid detergent to
heavy duty liquid detergent in addition to shampoos and conditioners.
 Able to differentiate between soap and detergent
 Able to understand the different type of surfactants and their characteristics
 Able to understand the role of surfactant in detergent, household and cosmetic
manufacturing
 Able to analyze formulated products
 Able to label a detergent product according to PS
 Able to choose the right mixing device to produce a good quality detergent product
 Able to produce lab scale product and be introduced to commercial scale detergent
production line
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Prof. Amer EL-Hamouz
4

Grading
Activity Percent (%)
Midterm Exam 25 %
Projects and Assignments 25 %
Final Exam 50 %
5

Expectations for Students
 Be on time
 Attend lectures, pay attention, listen and take notes.
 Hand in assignments and projects on time
 If you have a cell / mobile phone, please either turn it off or
place it in silent mode prior to class.
 ABSENCE FROM AN EXAM: Makeup exams will be given only
under extremely unusual circumstances.
6

Soap and Detergents
■ Soaps and detergents are essential to personal and public health.
 Through their ability to loosen and remove soil from a surface, they contribute
to good personal hygiene; reduce the presence of germs that cause infectious
diseases; extend the useful life of clothes, tableware, linens, surfaces and
furnishings; and make our homes and workplaces more pleasant.
 Soaps and detergents found in the home can be grouped into four general
categories:
1. Personal Cleansing,
2. Laundry,
3. Dishwashing and
4. Household Cleaning.
Within each category are different product types formulated with ingredients
selected to perform a broad cleaning function as well as to deliver properties
specific to that product. Knowing the different products and their ingredients
helps you select the right product for the cleaning job.
7

Soap & Detergent Products
1. Personal Cleansing Products:
 Include products for hand and body washing as well as shampoos,
conditioners, and toothpastes.
 They are marketed primarily in bar, gel, and liquid forms.
 A major consideration in formulation of such products is the desired
consumer aesthetic such as lather, skin feel, smell, and taste.
8

2. Laundry Detergents And Laundry Aids.
 These comprise mainframe laundry detergents in powder, liquid, tablet,
gel, and bar form.
 Laundry aids: fabric conditioner, pretreaters and bleaches.
 Typical laundry detergents are formulated to provide general cleaning,
the ability to maintain whiteness, brightness, softening, dye lock, ﬁber
protection, and disinfectancy.
9

3. Dishwashing Products
 These include detergents for hand and machine dishwashing and are
typically provided in liquid, gel, powder, or tablet form.
 Hand dish wash products are formulated to remove and suspend food soils
from a variety of surfaces, and they must be mild to skin.
 Products designed for automatic dishwashing must provide soil removal and
suspension, control of water hardness.
 Rinse aids are specialty detergent formulations for automatic dishwashing
designed to promote drainage of water from surfaces via lowering of surface
tension. This helps minimise spotting and ﬁlming during drying.
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4. Household Cleaning Products.
 Called “all-purpose” cleaners are designed to penetrate and loosen
soil, control water hardness, and prevent soil from redepositing onto
clean surfaces.
 Many of these products also contain low levels of antibacterial actives.
 Powdered abrasive cleaners remove heavy accumulations of soil via the
use of mineral or metallic abrasive particles.
 Some of these products may also bleach and disinfect .
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Soap
 Ordinary household bar soap or toilet soap is a mixture of long chain fatty
acids.
 The fatty acids containing 8 to 22 carbon atoms.
 Soap: any salt of fatty acid and usually made by saponification
of fatty oil with caustic soda.
 In most developed countries soap products are now relatively insignificant in
the domestic markets, except for the toilet soaps used for personal washing.
 In less developed countries, household soaps continue to be the main detergent
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Soap Raw Materials
 Raw materials
 Alkali (sodium hydroxide (lye) or potassium hydroxide)
 Fats (tallow) and Oils
Additives are used to enhance the colour, texture, and scent of soap.
Fragrances and perfumes are added to the soap mixture to cover the odour of
dirt and to leave behind a fresh-smelling scent
 Additives
 Optical brightener
 Chelating agent are used to surround unwanted metal ions found in
cleaning solutions like water hardness (phosphates, EDTA (ethylene
diamine tetra acetate), sodium citrate and zeolite compounds).
 Abrasive (enhance the texture of soap include talc, silica and marble
pumice)
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Characteristics of Soap
 Soaps are prepared by direct saponification of fatty acid (lauric, myristic,
palmitic, stearic and oleic) involving varieties of fatty acids in the fat, glycerol
(glycerine) being by product.
 In the process fats are splitted into fatty acid and glycerol and then the
separated fatty acids are neutralized to make soap.
 Theoretically for an average 100 kg of fat on saponification with 15.4 kg NaOH
yields 103.6 kg of pure sodium soaps and 11.8 kg of glycerol.
fat + 3NaOH → glycerine + 3 soap
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2/10/2020
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Characteristics of Soap…. continued
 The nature of soap depends mainly upon its component fatty acid from
which the soap is made.
 The solubility and hardness of sodium salts of various fatty acids differ.
 Hard soaps consists mainly of sodium oleate or sodium palmitate or
sodium stearate.
 Soft soap consists mainly of sodium and potassium salts of lauric and
myristic acids which are main composition of coconut oil and palm oil.
Soft soaps are more soluble than hard soaps.
 Ammonium soaps are more soluble than potassium soaps and potassium
soaps are more soluble than sodium soaps.
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Characteristics of Soap
 Various oils may produces soaps of various physical appearance, such as
creamy, greasy, waxy.
 Quality of soaps also varies, some having lasting lather, some have lather
vanishing immediately, some remain hard through absorbing water.
 So the character of water soluble soaps are mainly determined by nature of the
fats used in their preparation.
 Fats containing high percentage of lauric and myristic acid produce soaps
that are firm (solid) and readily soluble in cold water.
 These soaps have good foaming property and are not easily salted out.
Because of this property, they are used where washing water is saline.
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Characteristics of Soap…. continued
 Soft fats or oils such as olive, cottensead, linsead, soyabean and corn oil
containing high percentage of unsaturated acids produce soaps whose
solubility in lake warm water is quite good.
 These soaps are suggested to be used for washing delicate surfaces and
fibres.
 A mixture of hard fat such as tallow or similar fat, and soft fat such as coconut
oil/palm oil is usually used in the preparation of toilet soaps.
 The ratio of tallow to coconut oil being 60:40 approximately. Sometimes 7 to
10 percent free fatty acids are added to the mixture.
 Other factors affecting the physical properties are: moisture content, crystal
character, mechanical working in finishing process, cooling during solidification.
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For information
 Sodium laurate C12H23O2Na (sodium salt of a fatty acid (lauric acid))
 Sodium palmitate C16H31O2Na (Sodium palmate is synthesized by
reacting palm oil with sodium hydroxide)
 Sodium stearate C18H35O2Na (sodium salt of stearic acid)
Soaps can not be used in acid solution, Why?
Because it is decomposed with the liberation of fatty acid and it
forms a precipitate with the calcium and magnesium in hard water.
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Cleaning mechanism
 In solution the molecules of soap are dispersed in clusters, each of which may
contain hundred of soap molecules.
 Each molecule has one end polar “-COONa” and the other end is non polar,
the long chain of carbon.
 The polar end is soluble in polar solvent water and non polar end which is
insoluble in water is soluble in non polar ends of other soap molecules which
therefore clinch (settle) together at the centre of the cluster called micelle.
 Each polar end is surrounded by an ionic atmosphere. The repulsion between
similar charges keep the micelle dispersed.
 Soap molecules being big enough (each chain of mostly 12 to 18 or more
carbon atoms) each end clearly displays its own solubility behavior.
 Such dual solubility behavior gives soaps and detergent their cleansing power.
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Cleaning mechanism… continued
 Reducing soap interfacial tension, soap solution increases the wetting ability of
water which easily penetrates the fabrics and reaches the soil.
 Non polar ends of soap molecules dissolve in dirt holding grease and oils.
 The polar ends of molecules projecting in to the surrounding water layer keep
dirt as stable emulsion.
 Washing process thus removes the soil which is kept in the washing liquid as
emulsion, suspension in solution.
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How Soap & Detergent Work !!!
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The cleaning action of soaps and detergents
Dr. Majd Shhadi 23
Step # 1: You take the plate with some grease on it and dip it in sudsy water then agitate.
Step # 2: At the
molecular level the
detergent
molecules are
adsorbing onto the
grease,
Step # 3: your agitation
or scrubbing is
breaking the grease into
small droplets.
Step # 4: The role of the
detergent is to prevent the
droplets coalescing and
redepositing on the plate

Manufacturing steps
 Cleaning products come in three principal forms: bars, powders
and liquids.
 Some liquid products are so viscous that they are gels.
 The first phase in manufacturing all three forms is the selection
of raw materials.
Raw materials are chosen according to many criteria, including their human
and environmental safety, cost, compatibility with other ingredients, and
the form and performance characteristics of the finished product.
While actual production processes may vary from manufacturer to manufacturer,
there are steps which are common to all products of a similar form.
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Soap Manufacturing Process
 Boiling Process
 Continuous Process
 Cold & Semiboiled method.
 Soap and detergent manufacturing consists of a broad range of
processing and packaging operations.
 The size and complexity of these operations vary from small
plants employing a few people to those hundred workers.
 Products range from large-volume types like laundry detergents
that are used on a regular basis to lower-volume specialties for
less frequent cleaning needs.
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Soap Manufacturing
Sodium soaps can be made by:
1. Direct saponification, almost always with caustic soda.
2. Splitting, or hydrolysis of the fat with water to fatty acids plus
glycerol followed by the separation of the glecerol and the
neutralization of the fatty acids with caustic soda or sodium
carbonate to form soap.
1. Neutralization of the fatty acids produced in other ways,
particularly by the oxidation of a petroleum hydrocarbons.
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SOAP MANUFACTURING
Step 1 - Saponification
A mixture of tallow (animal fat) and coconut oil is mixed with sodium hydroxide
and heated.The soap produced is the salt of a long chain carboxylic acid.
Step 2 - Glycerine removal
Glycerine is more valuable than soap, so most of it is removed. Some is left in the
soap to help make it soft and smooth. Soap is not very soluble in salt water,
whereas glycerine is, so salt is added to the wet soap causing it to separate out
into soap and glycerine in salt water.
Step 3 - Soap purification
Any remaining sodium hydroxide is neutralised with a weak acid such as citric
acid and two thirds of the remaining water removed.
Step 4 - Finishing
Additives such as preservatives, colour and perfume are added and mixed in with
the soap and it is shaped into bars for sale.
27

Difference between Soap and Detergent?
 Soaps are produced from natural products, and detergents are
synthetic, or man-made.
 To make soap, the first step is to start with fats and oils that are
reduced to fatty acids and glycerine with a high pressure steam. The
fatty acids then combine with either sodium or potasium salts (an alkali
or base) to produce soap and water.
 After this process, the soap possesses a hydrophilic end that is
attracted to water and a hydrophobic end that is repelled by water,
allowing the soap to break down materials that dissolve in both oil
and water.
29

 Detergents are created through a similar process and produce an
almost identical product, a sodium salt.
 The first ingredient used in creating detergents is the compound
propylene, CH3-CH=CH2, which used to just be burnt off as waste by
the petroleum industry. Propylene molecules are manipulated to form a
compound that will react with sulfuric acid.
 Next, sodium hydroxide is added to neutralize the sulfuric acid
resulting in a sodium salt similar to the one present in soap. In general,
since soaps are a more natural product, they are used on the body,
and detergents are used on clothes. But detergents are the more
prevalent of the two and are often used in combination with natural
soaps.
30

■ Both soaps and detergents share a critical chemical property -
they are surface-active agents, or surfactants.
■ Soaps possess a number of qualities that make them preferable
to detergents. First, as mentioned earlier, they are:
– Natural products
– Less harmful to the human skin and the environment.
– Soaps are biodegradable and do not create pollution in our rivers
and streams.
■ Since the soap does not rinse out as well as detergent, it tends to
build up on clothes, and over a long period of time, causes the
fabric to deteriorate while leaving an odor.
■ Another shortcoming of soap is that it is less powerful than
synthetic detergent and tends to lose its cleaning power over
time. So don’t wash your laundry with soap
Prof. Amer EL-Hamouz 31

 Both soaps and detergents are used for cleaning.
 Soaps are made from natural fats and oils of plants and animals,
whereas detergents are synthetically manufacture.
 Soaps are soft and are thus used on our skin whereas detergents
are hard and used for washing clothes.
 Soaps do not cause to environment being biodegradable
32

Differences between Soap and Detergent
 Soap is a detergent, but the word “detergent” is frequently confined to non -soapy
surfactants and products based on them.
 These are called non soapy detergent (NSDs). These are called soapless detergents
or synthetic detergents.
33
Detergent
Soap
Better detergency with higher
emulsification power
Good detergency
Cleaning
Long chain composed of aliphatic
and aromatic organic compounds.
The functional groups may vary
from anionic, nonionic and
cationic
A long chain fatty acids salts of
alkali metals having anionic
functional group
Active Agent
They form soluble salt of Ca2+ ,
Mg2+ or at least keep insoluble
salt are formed it has the ability
to flocculate
Precipitate might form in hard
water reduce their cleaning
ability
Solubility of
Ca2+ , Mg2+

Differences between Soap and Detergent
34
Detergent
Soap
Because its salts of strong acid it
produces neutral solution
It can’t work under acidic
conditions
Acidic Conditions
Good for cotton but very low
penetrating ability for wool also
doesn't work for silk as the silk is
very sensitive to aromatic
compounds
Good cleaning power for cotton
and wool
Textile Texture
It has large number of products
due to its composition (anionic,
nonionic, cationic, amphoteric)
Because of its composition of
fatty acid and anionic group, it
has limited type of products
Varity of Products
May of detergents are not
biodegradable (are generally
synthetic)
Easily biodegradable
(are usually manufactured
(
using natural materials
Biodegradability

Assay number 1
 Prepare an assay about the soaps and detergents types exist
in the Palestinian market. You have to indicate:
1. Trade name of the product, function of the product and the
manufacturer name (local or international).
2. Price of the product, size of the product, monthly sale of the
product, year of introduction.
Due date:
35

Surfactants
 Surfactants are surface-active agents and their function is to
penetrate and loosen soil, enhance water absorption and wetting of
surfaces, suspend, disperse, and emulsify soil in water, and generate
and stabilize foam.
 The main function of surfactants is to reduce the interfacial tension of
solution which contain them.
 Surfactants contain Hydrophilic (water lover, Polar) and Lipohobic
(Hydrophobic, oil lover, non-polar) parts.
 The ratio of these two parts is called Hydrophilic- Lipohobic Balance
(HLB).
36

Surfactants
37

Surfactants
39

Surfactants
 Generally, surfactants are classiﬁed
according to their Hydrophilic
component as Nonionic, Anionic,
Cationic, or Amphoteric.
 As with all systems of classification
there are grey areas and some may
transcend (go beyond) the boundaries.
For example amine ethoxylates are
generally non ionic if the lipophilic is
long chain and cationic if it is a short
chain.
40

Anionic Surfactants
 They are the most commonly used surfactants.
 Anionic surfactants account for about 50 % of surfactant use in Europe
and about 60 % in the United States.
 Most are high-foaming but sensitive to hard water and therefore
require the addition of substances to complex calcium and magnesium
ions (i.e., detergent builders).
 They are more effective than other surfactants in particulate soil
removal, especially from natural fabrics.
 As a rule, they are easily spray-dried and thus are favored for
detergent powders.
 Very common surfactant is LABS (more digestible to bacteria)
41

Anionic Surfactants
 Sodium TetraPropylene Benzene Sulfonate (ABS) generally applied to the
branched-chain products, which are only biodegradable with difficulty.
 ABS is not used in developed countries except for specialty applications where
it will not reach natural waters (e.g., as an emulsifier for agricultural chemicals).
 Sodium 5-dodecylBenzeneSulfonate, (Sodium Salt, LAS)
 LAS has the lowest cost of any surfactant and is used throughout the world. It
is sensitive to water hardness.
42

Anionic Surfactants
 Alkyl Sulfates
 Foaming Agent
 Rapidly Biodegradable
 Sodium Lauryl Sulfate
They include:
 Alkylbenzene Sulfonates (Detergents)
 Linear Alkyl Benzene Sulfonate (LABS)
43

Anionic Surfactants
 (Fatty Acid) Soaps
 Lauryl Sulfate (Foaming Agent)
 Di-alkyl Sulfosuccinate (Wetting Agent)
 Lignosulfonates (Dispersants)
44
 Ether Sulfates

Anionic Surfactants
 Alkyl Ether Sulfate
(liquid Products)
 Olefin Sulfonates
 Alkanesulfonates
45

Cationic Surfactants
 Cationic surfactants are useful as fabric softeners, corrosion inhibitors, and
antimicrobial agents.
 They are not used in general purpose detergents because they do not provide
effective cleaning at neutral pH.
 They are adsorbed rapidly to textiles so that their solution concentration drops
very quickly to low levels, making them unsuitable for industrial processing
baths, although they see some specialty use in connection with anionic dyes.
 Except for applications where biological activity is critical, as in pesticides and
pharmaceuticals, only nitrogen-based compounds are used as cationic
surfactants.
 Cationic surfactants are generally rated as being more irritating to the skin
than anionic surfactants.
46

 A very large proportion of this class corresponds to nitrogen
compounds such as fatty amine salts and quaternary ammoniums, with
one or several long chain of the alkyl type, often coming from natural
fatty acids.
 These surfactants are in general more expensive than anionics.
 Examples on cationic surfactants:
 Quaternary ammonium salts such as:
Alkyl Trimethyl Ammonium Chloride R-N(CH3)+
3Cl-
Used as germicides, disinfectants in hard water especially against gram-
positive bacteria. The antimicrobial effect is deactivated in the presence
of anionics.
47

 Alkyl Quaternary Ammonium Salts
 Benzyl alkyl dimethyl ammonium Salts
 Called benzalkonium salts, these are widely used, especially in
pharmaceuticals.
 Both benzyl trialkyl and alkyl benzyl trialkyl compounds are common.
Typical products contain arrange of alkyl chain lengths.
48

 Amido amine Quaternaries
 Ethoxylated Acids (Polyethylene glycol, PEG Esters)
These can be considered to be esters of fatty acids and polyethylene
glycol, although they are generally made by direct addition of ethylene
oxide (EO) to the acid. They contain, besides the main monoester
ingredient, diester, free acid, and free PEG.
49

Non Ionic Surfactants
 These surfactants do not ionize in aqueous solution but they contain
hydrophilic-lipophilic ends to make them surfactants.
 The lipophilic portion is normally alkyl chain or an alkyl substituted
aromatic hydrocarbon.
 The hydrophilic portion is usually a polyglycol chain.
 Non-ionics account for roughly 40 % of worldwide surfactant use.
 Non-ionics are generally more tolerant than anionics of water hardness
(less demand for builders).
 They tend to be more effective than other surfactants for removal of
oily soil from synthetic fabrics.
50

 Most non-ionics are considered low-foaming products, have good cold
water solubility, and have a low critical micelle concentration,
making them effective at low concentration.
 Their compatibility with cationic fabric softeners makes them
preferable to anionics in certain formulations.
 They are more common in industrial applications than are anionics.
51

Non Ionic Surfactant
 Ethoxylated Alcohols, (i.e., Polyethylene glycol, PEG Ester) [R(OCH2CH2)nOH]
 The largest use of these compounds is in laundry detergents, where the
ethylene oxide (EO) chain length is usually in the range 7-9, although specialty
products may contain 30 or more moles.
 Ethoxylated Alkylphenols
 Most commercial products contain branched, rather than linear, alkyl groups.
 These compounds only slowly reach complete biodegradation upon release to
the environment.
 Foam stabilizer: specially used in shampoo
52 Prof. Amer EL-Hamouz

 Surfactants derived from sugar, such as alkyl polyglycosides (APG) (good
water solubility, good emulsifiers, good wetting and form profile. Their
biodegradability is excellent). Used for personal care cleaners such as
shampoos.
 Amine oxides, such as DMDAO (dimethyl dodecyl amine oxide) and
CAPAO (cocoamidopropyldimethyl amine oxide).
 This type of surfactant is non-ionic at pH values above its pKa and
cationic below that point (about pH =3).
 When functioning as a non-ionic, amine oxides have many useful
properties.
53

Non-ionic Detergent
 They interact strongly with anionics which can result in performance
benefits (foam, surface tension especially in hand dishwashing liquids).
 Amine oxides help to mitigate anionic surfactant irritation, act as foam
stabilizers (more creamy), and can also function to improve grease
removal.
Hydroxyl group & alkyl Phenol are the main raw material
Foam stabilizer specially used in shampoo
This an example of how nonionic surfactant is prepared
54

Amphoteric Surfactant
 These can ionize as either anionic or cationic substances, depending
upon the alkalinity (anionic), or acidity (cationic) of the solution in
which they are present.
 They are very expensive and are used in a specialized products
(such as cosmetics).
 They contain both anionic and cationic functions in the same molecule.
 More costly to produce than ionic surfactants, amphoteric surfactants
represent only about 3 % of surfactant volume in Europe and less than
1% in the United States.
55

Amphoteric Surfactant
 They are less irritating than other materials and are largely used in
personal care products (i.e., baby shampoo).
 Examples
 Alkyl amino Acids
 Alkyl betaines
 Alkyl amido betaines
Amido betaines are the most commercially important betaines. They tend
to be high foaming.
Have good detergent properties, and are outstanding in their lack of
irritation to skin and eyes.
56
Alkyl Betaines

Kind of Detergent …. Summary
 Anionic Detergent
- Fatty alcohol & Alkylbenzene are main raw materials
- Used for less foam
 Cationic Detergent
- Used in Powder & Paste detergent
- Good in Detergency
- Wetting, Foaming and Emulsifying properties
57

Comparison
Amphoteric
Cationic
Nonionic
Anionic
Desired
Property
Better
Poor
Good
Best
Foam
Good
Fair
Good
Better
Detergency
Best
Poor
Good
Variable
Mildness
3 % Europe
1 % USA
4 %
40 %
50 % Europe
60 % USA
Production
58

Combination On Non Ionic And
Anionic Surfactants
When non ionic surfactant is used in combination with anionic surfactants
they provide benefits to the overall formulation, such as:
 Mildness, improved wetting, foam boosting, and foam stabilization.
Some non-ionics that are found in Light-Duty Liquid Detergents (LDLDs) are
ethoxylated alcohols, in particular 11-carbon (C11-hydrophobe) chains with
9 moles of ethoxylation (e.g., Neodol 1-9 from Shell).
59

Combination On Non Ionic And
Anionic Surfactants
Focused on:
 The ability to remove and emulsify the suspended soil.
 Foaming and foam stability in the presence of soils.
 Solubility in the aqueous phase.
 The ability to coexist with other ingredients under extreme conditions as
well as at room temperature.
 A good environmental profile
60

An-Najah National University
Faculty Of Engineering And Information Technology
Department of Chemical Engineering
Surfactants: Part 2
SURFACTANTS IN SOLUTION
First Semester 2017/2018

4 nm
Unimers
Normal micelles
spherical
cylindrical
Bilayer lamella
Reverse micelles
Inverted hexagonal phase
Surfactant Aggregates
Molecules of amphiphilic surfactants in solution self-assemble into various supramolecular
aggregates. This slide shows typical changes in surfactant self-assembly and morphologies
formed with decreasing water content in the system (water content decrease is shown by
arrows)

63
Unimers

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0
2
4
6
8
10
12
14
0 1
Surfactant concentration
CMC

Critical Micelle Concentration
CMC
• Below CMC only
unimers are present
• Above CMC there are
micelles in equilibrium
with unimers

Solution Properties
0
2
4
6
8
10
12
14
0 1
CMC
Concentration
unimers
micelles
0
2
4
6
8
10
12
14
0 1
CMC
Osmotic pressure

0
2
4
6
8
10
12
14
0 1
CMC
Isc Light scattering
66

Solubilization
67
• Spontaneous transfer of a compound insoluble in the bulk
solvent into solution due to incorporation into the surfactant
micelles.
polar compound
Reverse micelles
non-polar compound
Normal micelles
amphiphilic compound

Solubility Effects
68
Solubility of a poorly soluble
compound increases as a result of
solubilization in the micelles
0
2
4
6
8
10
12
14
0 1
CMC
Solubility
One method to characterize CMC of a surfactant in aqueous solution is
to determine solubility of a water-insoluble dye as a function of
surfactant concentration. Above CMC the dye is transferred into
solution due to incorporation into the core of the micelles.

What do we mean by surfactant
SELECTION
First - selecting between the available chemical types:
 Anionic: Negative charge
 Cationic: Positive charge
 Amphoteric: Charge depends on pH
 Nonionic: No charge
Second – once having selected the chemical family –You must
select a surfactant or surfactant pair with the correct solubility
for your unique application.

SELECTION
70
 How does surfactant solubility affect performance?
For example ( very general rules)
 You need high water solubility for cleansing and detergency
 You need medium solubility for spreading and dispersion.
 You need low solubility for invert emulsions and coupling
immiscible oils.
 You need a blend of solubilities for Oil/Water (O/W)
emulsions

SELECTION
71
Is there a way to predict surfactant solubility by merely looking
at its chemistry?
Yes ( for the most part )
 Almost all “soaps” have medium to high solubility in water &
low solubility in oils/fats.
 Almost all anionics such as Sodium Lauryl Sulfate (SLS) are
highly water soluble & low solubility in oil/fats.
 Almost all cationics and amphotrics are highly water soluble.
 Nonionics’ water solubility can be predicted by their HLB.

What do we mean by “HLB”
72
 All surfactants must have an oil loving portion and a water loving
portion or they would not have surface activity.
 The ratio of the oil loving portion to the water loving portion is
what we call its balance.
 We measure this balance based on molecular weight.
 “HLB” stands for – HYDROPHILE / LIPOPHILE / BALANCE
 The “system” was created as a tool to make it easier to use
nonionic surfactants. In general it applies to nonionic surfactants
only.

Why use the HLB System
73
 It tells us something about the chemistry of the surfactant.

 When you know about the chemistry of the surfactant you can
predict how it will behave.
 Being able to predict how a surfactant will behave will save you
time ($$$$$).

What is the HLB “system” ?
74
The basic principle of the system is:
 Surfactants have an HLB value.
 The higher the number, the more hydrophilic (water soluble).
 The lower the number, the more lipophilic (oil soluble).
 Applications for surfactants have an HLB requirement.
 Matching the requirement with the value saves time and money.
 It was/is intended as a large scale road map to good
emulsification performance.

75
 Matching the HLB requirement with a surfactant’s HLB value yields
optimum performance.
 The balance between the hydrophilic and lipophilic properties of
the molecule (HLB) is used to optimize detergent and emulsifying
properties.
 The solubility of nonionic surfactants in water can usually be used
as a guide in approximating their HLB and their usefulness.

How do we determine the HLB “value” of a
surfactant ?
76
 We calculate the water loving portion of the surfactant on a
molecular weight basis and then divide that number by 5.
 This keeps the HLB scale smaller and more manageable
 The working scale is from 0.5 to 19.5
 This number is then assigned to the nonionic surfactant.

77
How do we determine the HLB “value” of
a surfactant ?

Emulsifier
you will use a "water-soluble" emulsifier or blend to make an
O/W emulsion, or to solubilize oils, or to obtain detergent
action.
In other words, you use a "water-soluble" emulsifier when you
want your final product to exhibit aqueous characteristics, i.e.
to dilute readily with water.
If you wanted to make a W/O emulsion, or couple water soluble
materials into an oil, or produce some other type of non-
aqueous emulsion system, you would choose an oil-soluble
emulsifier.
78

EMULSION TYPES
Emulsions are classified as:
Oil-in-water (o/w)
 The continuous phase is water
 Dispersed oil droplets.
 med / high HLB requirement
Water-in-oil (W/O) Invert
 The Continuous Phase Is Oil
 Dispersed Water Droplets
 Low HLB Requirement
Dr. Majd Shhadi
79
Milk
Hand Cream

Phase I
Phase II
Surfactant
A. Two immiscible liquids, not emulsified
B. Emulsion of Phase II dispersed in Phase I
C. The unstable emulsion progressively separates
D. Surfactant positions itself on interface between
Phases I and II, stabilizing emulsion.

An example of an HLB value calculation
 BRIJ ® 98 INCI name : oleth-20 is a 20 mole ethoxylate of oleyl
alcohol
 Calculate the molecular weight of the 20 moles of ethylene oxide
(one mole ETO =44 );
20 x 44 = 880
 Add this number to the molecular weight of the oleyl alcohol;
880 + 270 = 1150 ( the mol. wt of BRIJ 98 )
 What percentage of 1150 is 880 ?
880/1150 = 76.5%
 76.5% divided by 5 = 15.3
15.3 is the HLB value of BRIJ 98
81

DETERMINING HLB BY CALCULATION
For the surfactant CH3(CH2)17-(OCH2CH2)3OH
 First find the formula weight of the molecule = 403
 MW of head group = 44 X 3 + 17 = 149
 HLB = (MW of head group/MW of molecule) * 20 = 7.4
 HLB = (149/403) * 20 = 7.4
For the molecule:
 For the surfactant CH3(CH2)17-(OCH2CH2)20OH
 MW of molecule = 1150
 MW of head group = 44 X 20 + 17 = 897
 HLB = (MW of head group/MW of molecule) * 20
 HLB = (897/1150) * 20 = 15.6
You should observe the increase in HLB as the head group becomes
more polar.
Dr. Majd Shhadi
82

Important to remember !
 The HLB value is an indication of the solubility of the surfactant.
 The lower the HLB value the more lipophilic or oil soluble the
surfactant is.
 The higher the HLB value the more water soluble or hydrophilic the
surfactant is.
 This surfactant solubility property is an indicator of its likely end
use.
 HLB values are calculated for nonionic surfactants only.
 The HLB value is the molecular weight percent of the water loving
portion of the nonionic surfactant - divided by five.
83

Examples of matching HLB values to application
needs
 Mixing unlike oils together
Use surfactants with HLB’s of 1 to 3
 Making water-in-oil emulsions
 Wetting powders into oils
 Making self emulsifying oils
 Making oil-in-water emulsions
Use surfactant blends with HLB’s of 8 to16
 Making detergent solutions
 For solubilizing oils ( micro-emulsifying ) into water
Use surfactant blends with HLB’s of 13 to 18
84

Examples Of Matching HLB Values To Application
Requirements
85
HLB
Range
Application
Water Solubility
1-4
Compatibilizing Dissimilar
Oils
antifoams
No dispersability in water (no
emulsion)
3-6
Water-in-Oil Emulsifiers
Poor dispersability (emulsion)
6-8
Wetting powders into oils
Milky dispersion after
agitation
8-10
Oil-in-Water Emulsifiers
Stable milky dispersion
10-13
Detergents
Translucent to clear dispersion
13
(Hydrotrope)
Solubilizers
Clear solution

HLB Griffinˊs Scale
 It is an arbitrary
scale between 0 and
20 which expresses
numerically the size
and strength of the
polar portion relative
to the non-polar
portion of the
molecule.
86

Moles Ethylene Oxide, EO
87
 Most of the Nonionic surfactant have as their hydrophilic group is
the series of ethylene oxide (EO) chain.
 The larger this portion of the molecule, the more water soluble
is the non-ionic surfactant.
 Ethylene oxide is the reactive chemical added to base alcohols
and amines to form ethoxylated Nonionic surfactants.
 Usually in the naming of these substances the number of ethylene
oxide per mole of lipohile is indicated by the number followed by
EO
 Example: Nonyl Phenol Ethoxylate (9EO), NP9

88
HLB & EO
HLB
 From 0-40
 Low HLB more oil soluble
3-6 Water in oil emulsifier
7-9 Wetting Agent
8-15 Oil in water emulsifier
12-15 Detergency
15-18 Solubilizer
EO
1-3 Emulsify small amount
of water in oil
4-6 Emulsify small amount
of oil in water
7-12 Cleaning action
> 12 Special properties
such as solubilizing

89

Calculation of Ratio of Emulsifier to Produce A
Particular Required HLB Value
 Surfactant blends are commonly used to obtain desired emulsifying
properties.
 Combinations of emulsifiers can produce more stable emulsions than
using a single emulsifier with the same HLB number.
 One of the most important aspects of the HLB system is that HLB
values are additive if the amount of each in a blend is taken into
account.
 Thus, blends of high and low HLB surfactants can be used to
obtain the required HLB of an oil.
Dr. Majd Shhadi
90

Calculation of Ratio of Emulsifier to Produce A
Particular Required HLB Value
 The HLB value of a combination of emulsifiers (surfactants) can be
calculated as follows:
HLB required = X HLBA + (1-X) HLBB
 Where X fraction of A
 Rearrangement the above equation in percent (%) form will be
Amount of material A required = 100 (HLB required - HLBB)/ (HLBA– HLBB)
B = 100-A
Dr. Majd Shhadi 91

HLB: Calculation
 What is the HLB of the mixture of 40 % Span 60 (HLB = 4.7)
and 60 % Tween 60 (HLB = 14.9)?
Solution
Assuming A: tween 60 , B: span 60
A = 100 (X – HLBB )/(HLBA – HLBB)
60 = 100 (x – 4.7) / (14.9 – 4.7)
60 = 100x – 470 / 10.2 X = 10.82
92

HLB of Surfactant Blend
 Spans are sorbitan fatty acid esters having low HLB values
ranging from 1.8 to 8.6.
 Tweens are polyoxyethylene derivatives of spans. So, they are
more hydrophilic having higher HLB values ranging from 9.6 to
16.7.
 Span 60 (HLB = 4.7)
 Tween 60 (HLB = 14.9)
 Span 80 (HLB = 4.3)
 Tween 80 (HLB = 15.0)
93

Sorbitan monostearate is
an ester of sorbitol and
stearic acid (synthetic
wax) (Span 60)
Polyoxyethylene sorbitan
monooleate (Tween 80)
Sorbitan monooleate ethoxylate
2/10/2020
94

Required HLB
 HLB needed for emulsification of the oil phase. If there are
several oil ingredients the required HLB is calculated as a sum
of their respective required HLB multiplied by the fraction of
each.
 Calculate the required HLB for the oil phase of the following o/w emulsion:
cetyl alcohol 15 g., white wax 1 g. Lanolin 2 g, emulsifier (q.s.), glycerin 5 g.
water 100 g.
Required HLB Fraction
(from reference)
Cetyl alcohol 15 x 15/18 12.5
White wax 12 x 1/18 0.7
Lanolin 10 x 2/18 1.1
Total required HLB 14.3
95

HLB: Calculation
In what proportion should Span 80 (HLB = 4.3) and Tween 80 (HLB =
15.0) be mixed to obtain “required” HLB of 12.0?
Solution
4.3 (1-x) + 15 x = 12 x = 0.72
72 % Tween 80 and 28 % Span 80
96

Glycerol Monostearate
 HLB value of 3.6~4.2
 Dissolves in hot grease, paraffine, ethanol, chloroform,
acetone and aether, the material is widely used when
producing of chocolate, margarine, ice cream, skin care
balsam, cold cream, hair oil and drug ointment, also
lubricant for plastic processing
97

Directions for using the HLB system to
select surfactants for an O/W emulsion
 Look at your formula
 Determine which are the oil soluble ingredients.
This does not include the emulsifiers
 Weigh each of the weight percents of the oil phase ingredients
together and divide each by the total.
 Multiply these answers times the required HLB of the individual
oils.
 Add these together to get the required HLB of your unique blend
98

For example
99

2/10/2020
100

2/10/2020
101

Calculations for HLB of this
unique blend
102

How do we use this information
to our advantage?
 We know that as a starting point we should select a surfactant
system with an HLB value of ~11.2
 For the surfactant system we recommend that you use a blend of
at least two surfactants.
– REASON
 Experience has shown the benefit
 Mixtures of a low HLB and a high HLB surfactant
 Give better coverage at the interface
 A blend of two surfactants is typical
103

An-Najah National University
Faculty Of Engineering And Information Technology
Department of Chemical Engineering
DETERGENT INGREDIENTS
First Semester 2017/2018

COMMON DETERGENT INGREDIENTS
 Modern detergents can comprise 20 or more ingredients
depending on what beneﬁts the detergent is meant to
deliver.
1. Surfactants
2. Dispersing Polymers
3. Builders and Chelants
4. Bleaching Systems
5. Solvents
6. Performance Enhancing Minor Ingredients
10
5

Surfactants
 Surfactants are primarily responsible for:
1. Wetting the surfaces of fabrics.
2. As well as the soil (reducing surface and interfacial tension),
helping to lift the stains off the fabric surface.
3. Stabilizing dirt particles and/or emulsifying grease droplets.
106

Dispersing Polymers & Antiredeposition Agents
 Are used in for avoiding incrustation and soil redeposition.
 In general two types of polymeric dispersants are used in
detergent formulations:
1. Polymers comprising ionically charged groups.
2. Nonionic polymers: include polyethylene glycol, polyvinyl
alcohol.
Typical of the ionic dispersing polymers are Water-soluble Linear
Polycarboxylates
107

Dispersing Polymers & Antiredeposition Agents
Polycarboxylates
 Comprise two types of polymers: homopolymers of acrylic acid and
copolymers of acrylic/maleic acid.
 Are used in low-phosphate and phosphate-free detergents.
 Are widely used in laundry (powder) detergent formulations.
where they assist in cleaning by acting as a dispersant for soil and
inorganic salts, provide alkalinity control, and serve as crystal
growth inhibitors.
 Carboxymethyl cellulose (CMC) an anionic dispersing polymer
 Cationic dispersants are less commonly used.
108

Builders
They enhance or “build” the cleaning efficiency of the
surfactant. Builders are designed to do the following:
1. Soften water by binding the hard water minerals.
2. Help surfactants concentrate on removing soil from fabrics.
3. Increase the efficiency of the surfactant.
4. Provide a desirable level of alkaline to aid in the cleaning
process.
5. Disperse and suspend soils so they cannot redeposit
themselves on the clothing.
 Builders: are any number of materials whose primary
function is the removal of Ca2+ and Mg2+ ions from aqueous
solutions. 10
9

Builders
 Sodium tripolyphosphate (STPP) is among the best known and widely
used detergent builder.
 In laundry detergent formulations it serves not only as an extremely
effective calcium control agent but also provides dispersion,
suspension, and anti-encrustation beneﬁts.
 Disadvantage: environmental concerns associated with large-scale
release of phosphates into the environment lead to the development of
a number of substitutes.
 Citric acid and sodium nitrilotriacetate are representative of soluble
detergent builders.
 Ethylene-diamine-tetraacetate (EDTA).
110

Builders: Mechanism
The primary function of builders is to reduce water
hardness. This is done either by:
 Sequestration or chelation (holding hardness
minerals in solution). Example: Complex phosphates
and sodium citrate.
 Precipitation (forming an insoluble substance).
Example: Sodium carbonate and sodium silicate
 Ion exchange (trading electrically charged
particles).
Example: Sodium aluminosilicate (zeolite A).
111

Builders
Builders are used in general purpose laundry powders and liquids
but not in light duty detergents (powders or liquids).
Most general purpose liquids contain builders such as citrate, but
some are unbuilt.
The unbuilt liquids use surfactants which are less hardness
sensitive, instead of including a builder to minimize interactions with
water hardness minerals.
Common builders used in liquid detergents are sodium and
potassium polyphosphates
112

Bleaching Systems
 Bleaches are common components of laundry, automatic dish wash,
and hard surface cleaning detergent formulations.
 They act to destroy chromophoric groups responsible for color in soils
via oxidative attack.
 Types:
1. Chlorine-based bleaches: are common in some powdered abrasive
hard surface cleaners and automatic dishwashing products
(Hypochlorite Bleach)
2. Peroxide-based bleaches: Hydrogen Peroxide
3. Activated peroxide systems
4. Metal catalysts
113

Hydrotrope
 A hydrotrope is a substance that improves the solubility of
surfactants in water, particularly those systems containing high levels
of builders or alkalinity.
 Are often added to an Light Duty Liquid Detergents (LDLD) to help
solubilize certain surfactants or other materials that are not easily
soluble in water to ensure the stability of the formulation.
 The addition of hydrotrope affect the formula viscosity and
cloud/clear points.
 Common hydrotropes are sodium xylene sulfonate (SXS), sodium
toluene sulfonate (STS), sodium cumene sulfonate (SCS) and
ethanol
114

Hydrotope
 The choice of hydrotrope is based on the builder levels and
requirements for each specific application.
 The following phosphate ester-based products are particularly
efficient hydrotropes.
 TRITON H-55 surfactant: solubilizes surfactants into moderately to
highly built detergents.
 TRITON H-66 surfactant (readily biodegradable): solubilizes
surfactants into low to moderately built detergents; solubilizes low-
foaming nonionic surfactants into highly built detergents.
116

Hydrotope
 TRITON QS-44 surfactant: solubilizes surfactants at use-
concentration levels and into low built detergents; provides
surface activity (e.g., detergency, wetting, foaming).
 DOWFAX C6L Surfactant: Solubilizes surfactants at use-level
concentrations, especially useful in the presence of hypochlorite
bleach.
117

Solvents
 The selection of solvents for use in detergent formulation depends on:
1. The nature of the actives being formulated.
2. The intended application of the detergent.
3. Economics.
 Water is the dominant solvent in most household and industrial
cleaning formulations. Generally water-based detergents are less
toxic, more environmentally friendly, cheaper, more surface
compatible, and easier to handle than petroleum-based solvents.
 However, many common detergent actives have limited solubility in
water requiring formulation of a co-solvent (ethanol, glycerol)
and/or hydrotrope.
118

Solvents
There are applications where water must be avoided.
 Dry cleaning of ﬁne textiles like silk and wool (volatile organic
solvents), it is not environmental safe.
Alternative: condensed phase CO2
 The cleaning of certain metal parts and electronic circuit boards.
Here chlorinated hydrocarbons like perchloroethylene or
methylene chloride, or volatile organics like methyl ethyl ketone
have historically been used but regulatory pressure has resulted in
a shift to more environmentally friendly solvents like terpenes and
dibasic esters.
119

Performance Enhancing Minor Ingredients
Depending upon the end use of the detergent formulation and the
beneﬁts to be delivered a number of performance enhancing minor
ingredients may be used. These include:
1. Enzymes
2. Brighteners/fabric whitening actives
3. Foam boosters
4. Antifoam agents
5. Thickeners
6. Soil release polymer
120

Minor Ingredients: Enzymes
Enzymes: promote soil removal by the catalytic breakdown of speciﬁc
soil components.
Proteases: (enzymes that degrade protein (blood)) are the most
common of all the detergent enzymes.
Others
Amylases: (starch degrading): acts on starchy soils (e.g., gravy).
Lipases: (lipid degrading)
Cellulases: (cellulase degrading) for removing pills from cotton fabrics,
thereby restoring the reflectance of the fabric surface and making
colors look brighter for cotton.
Enzymes are NOT compatible with Sodium Hypochlorite or Chlorine
release agents.
121

The Difference Between Bio and Non-Bio
Detergent
The essential difference between bio and non-bio detergents is that
bio detergents contain certain enzymes that are very effective at
cleaning stains.
These enzymes, designed to break down protein, starches, and fat
that are often found in food stains, sweat and other common stains.
The enzymes also work at lower temperatures, so bio detergents are
more effective at lower temperatures (30-50°C) than non-bio
detergents.
Non-bio detergents contain no enzymes, so there is a reduced risk of
irritating sensitive skin.
122

Brighteners/Fabric Whitening Actives
 Optical brighteners are colorless fluorescent whitening agents that
absorb ultraviolet radiation and emit bluish light, making fabrics
look whiter and brighter to the human eye.
 The most commonly used whiteners in laundry detergents are the
derivatives of 4,4-diaminostilbene-2,2-disulfonic acid.
123
Minor Ingredients: Optical brighteners
Laundry detergent fluorescing
under ultraviolet light

 An additive used in detergents (hand dishwashing and shampoos)
to generate a large-volume and stable foam.
 While most surfactants are capable of generating and sustaining
foam in the absence of soil, these foams rapidly collapse in the
presence of soil, especially fatty soils.
 In applications where foam must be maintained throughout the
course of detergent use, speciﬁc boosters may be added.
 While there is no direct correlation between foam and cleaning,
consumers in general use foam volume and foam persistence to
judge the performance of an LDLD.
124
Minor Ingredients: Foam Boosters

 Alkanol amides, particularly mono- and diethanolamides, are
effective foam stabilizers used in dishwashing liquids and
shampoos.
 LMMEA (lauric/myristic monoethanol amide).
 Amine oxides: DMDA (dimethyldodecyl amine oxide).
 Cocamide DEA, Cocamide MEA (Cocamide DEA showed a high
irritation potential).
125
Minor Ingredients: Foam Boosters

Minor Ingredients: Antifoam Agents
 Antifoam Agents: In many applications (automatic dishwashing) it
is desirable to minimize foam generation.
 Antifoam agents act to reduce or eliminate foams. They either
prevent formation of the foam or accelerate its collapse.
 Alkyl ethoxylate nonionic surfactants are commonly used as foam
control agents in detergents where application temperatures
exceed the cloud point of the surfactant (the temperature at which
the surfactant becomes insoluble).
126

Minor Ingredients: Thickeners
Thickeners: It is often desirable to modify the rheology of a
detergent formulation to ﬁt a particular application.
Thickening can be achieved through the use of:
 Inorganic Electrolytes (NaCl)
 A High-molecular-weight polymer like carboxymethyl cellulose
(CMC), guar, or xanthan gum.
 The Carbopol® series of polymers.
127

Minor Ingredients: Soil Release Polymers
Soil Release Polymers
Soil release refers to the enhanced removal of soil from a surface
as a result of modification of that surface with a specific agent,
typically a polymer that alters surface polarity thereby decreasing
adherence of soil.
Carboxymethyl cellulose (CMC): absorbs onto cotton fabric owing to
the similarity in structure between the cellulose backbone of CMC
and the cellulose polymer of cotton fibers. Once absorbed, the
carboxyl moiety creates a high net negative charge on the fabric
surface effectively repelling negatively charged soils, especially
clays.
128

Minor Ingredients: Fragrances
Fragrances provide three functions, regardless of the scent used.
1. They cover the chemical odor of the detergent
2. The odor of soils in the washing solution.
3. Plus, they impart a pleasant scent to fabrics, thus reinforcing the
clean performance.
 Additionally, a fragrance contributes to the character of the product.
 Some detergents are offered in unscented versions, appealing to
consumers who prefer low or no scent on laundry.
 They may also appeal to people whose skin is sensitive to fragrance
ingredients.
129

Chapter 7
Light-Duty Liquid Detergents
In this chapter, we will concentrate on:
 Typical compositions and ingredients, the hand
dishwashing process and the chemistry involved, test
methods and performance evaluations, formulation
technology, and new products and future trends.
130

Light Duty Liquid Detergent (LDLD)
 Light-duty Liquid Detergents (LDLDs) are mixtures of surfactants
dispersed in water and, as opposed to heavy-duty liquid
detergents (HDLDs), are free of builders or alkaline inorganics.
 Used for dishes, glasses, pots, pans, washing hands, cleaning
kitchen countertops, stove surfaces. Less often for washing
delicate fabrics.
 Consumers expect LDLDs to clean, foam, and be mild to their
hands.
131

 Long-lasting foam, pleasing appearance and fragrance, ease of
rinsing, safety for dishes, consumers, and the environment,
convenient packaging and ease of dispensing, and good value.
 In the developed markets, LDLDs are now more and more
concentrated, some are antibacterial for those concerned about
family health, and some are more experiential.
 In the developing markets, LDLDs are in general more dilute with
lower active levels and generally do not have the added
benefits (such as antibacterial ability)
132

 However, the fundamental consumer need is still a dishwashing
liquid that cleans fast, is convenient to use, and is not too
expensive.
 The LDLD market is worth over $900 million in the U.S.
133

Typical Composition and Ingredients of
LDLD
 Main ingredients are for cleaning, foaming, solubilization,
preservation, fragrance, color, and in some cases antibacterial
action.
 Surfactants are the main active ingredients in an LDLD formulation
and usually make up the bulk of the solids.
134

A Typical Light-Duty Liquid Composition
135
135

Typical Chemical and Physical Properties of
LDLD
Characteristic Typical Value
Viscosity, cP 100-500
pH 5-8
Cloud Point, oC less than 5
Clear Point, oC Less than 10
Solid level, % 10-50
Specific Gravity 1.0-1.1
136

Main Ingredients Ingredients in LDLD
 The type of surfactants typically used in LDLDs are anionics and
to a lesser degree nonionics and amphoterics.
 Cationics have not been used historically because of their lesser
cleaning ability and incompatibility with anionic surfactants.
 Table 7.3 summarize some of the surfactants and their structures
falling into these three classes (anionic, nonionic, and amphoteric)
that are found in LDLDs.
 Anionic surfactants have been used predominantly because of
their availability, good cleaning properties, excellent foaming
properties, and low cost.
137

Minor Ingredients in LDLD
 Preservatives are often needed to prevent microbial and fungal
growth in LDLDs.
 Preservatives commonly used are formaldehyde, gluteraldehyde,
benzoic acid, Kathon ®, Dowicil ®, Bronopol®
 Chelants are used to ensure that no precipitation occurs on aging.
The most common problem is iron, which introduced as an impurity
from surfactants and salts.
 The chelants most commonly used are EDTA, HEDTA, citrate salts,
and disodium diethylene pentaacetate
139

Chapter 8
Heavy-Duty Liquid Detergents
 Heavy-duty liquid detergents (HDLDs) were introduced into the
laundry market many years after the introduction of powder
detergents.
 In formulating a heavy-duty liquid (high levels of builders and
relatively low levels of surfactants; 15 %), therefore, the major
technical objective was to find ways of stably incorporating
maximum levels of builder salts.
 They are really tough, burnt-on soiled dishware.
 Required properties are alkaline (pH > 8), might be thickened
with a polymer thickener, and may contain a soluble abrasive.
140

Chapter 8
HDLDs have several advantages when compared to powder
detergents:
 Liquid detegents readily dissolve in warm or cold water, leaving
no detergent residue on dark fabric.
 They can be easily dispensed from the bottle or refill package.
 Liquids don’t suffer from adverse effects after exposure to
moisture (powders can ‘cake’ in storage when exposed to high
humidity).
 Liquid detergents providing a convenient way to facilitate the
removal of tough stains.
141

Which is better Liquid or Powder Detergent ?
 With the exception of fabric softeners and shampoos, the solid form
of cleaning products preceded the liquid form.
 This is true of manual and automatic dishwashing, laundering, and
general personal cleansing products.
 Soiling, water hardness, and temperature — are same for both
types.
 Cleaning performance is a function of concentration and type of
active ingredients that are delivered into the cleaning bath.
 Formulation problems are most severe when the active components
are less stable in an aqueous environment than in a solid matrix.
142

Chapter 8
Atypical heavy-duty liquid consists of all or some of the following
components:
 Surfactants, builders, enzymes, polymers, optical brighteners,
bleaches and fragrance.
 In addition, it may contain other special ingredients designed for
specific functions (buffers (alkaline pH), defoamers, hydrotropes
and preservatives).
143

Heavy-Duty Liquid Detergents (LDLD)
 Both an anionic and nonionic surfactants.
 Linear allylbenzene sulfonate (LAS) (anionic surfactants), alcohol
ethoxylates (nonionic surfactants), and alkyl ether sulfates
(anionic surfactants) are three of the most widely used
surfactants in liquid laundry detergents.
1-Linear allylbenzene sulfonate (LAS): the dominant surfactant
used in laundry detergents.
144

2. Alcohol ethoxylated  nonionic surfactant
 The high aqueous solubility of alcohol ethoxylates makes them a
useful ingredient in unstructured liquids.
 Excessive use of nonionic surfactants cause phase separation of
HDLD.
 Studies have shown that product containing:
LAS + alcohol ethoxylates  lower the CMC  provide
improvements in the detergency.
145

 Builders are formulated into detergents mainly to sequester
hardness ions (Ca2+, Mg2+) found in water, as well as to disperse
the dirt and soil particulates in the wash water.
 Common builders used in liquid detergents are:
 Sodium and potassium polyphosphates.
 Carbonates, aluminosilicates (zeolite A), silicates, citrates, and
fatty acid soaps.
146

 HDLD includes protease enzyme to digest protein soils such as blood
and proteinaceous food stains.
 Also it contains amylase enzymes which acts on starchy soils (e.g.,
gravy).
 Cellulase is also added to the formula.
147

Polymers in HDLD
 Low molecular weight polymer, water-soluble polyacrylate
dispersants prevent clay/particulate soils from redepositing on
fabrics.
 Soil release polymers facilitate the removal of oily/greasy soils
from synthetic fabrics and blends.
148

It may be classified into two main types:
 Unstructured liquids
 Structured liquids.
 Nonaqueous liquids
149

Structured Liquid Detergent
 Liquids containing high levels of anionic surfactants and electrolytic
builders from liquid crystalline surfactant phase.
 This is accelerated by the use of longer or branched chain, or using
higher electrolyte level.
 The resulting liquid is opaque, extremely thick, unpourable, and
frequently physically unstable.
 These products are formed when surfactant molecules arrange
themselves as liquid Crystals.
150

 It may also subsequently separate into two or more layers or
phases: a thick, opaque surfactant-rich phase containing the
flocculated liquid crystals and a thin, clear electrolyte-rich phase.
 The challenge in developing a liquid:
1. Prevent phase separation of the product.
2. Reduce the viscosity to a pourable level.
 Viscosities of commercially available structured liquids vary from
500 to 9000 cP.
151

 The liquid crystalline phase is in the form of spherical lamellar
bilayers or droplets. Contain layers of surfactant and water.
152

153

Unstructured Liquid Detergent
 Unstructured liquids, on the other hand, are usually thin, clear or
translucent, and are formed when all ingredients are solubilized in
an aqueous media and are the most widespread type of liquid
detergent sold on the U.S. market.
 Are commonly formulated with higher amounts of surfactants in
conjuction with lower builder levels, in contrast to structured
liquids, which utilize more builders and electrolytes.
 The physical stability of structural liquids are very dependent on
surfactant ratio, whereas the clear, unstructured liquids allow for
greater flexibility in choosing surfactant types/ratio as long as a
single phase is maintained.
154

 Structured liquids have the ability to suspend undissolved and
insoluble solids. The unstructured clear liquids, by their very nature,
don’t permit the use of insoluble materials.
155

156

Nonaqueous Liquids
 A third type of liquid detergent is one where the continuous
phase is nonaqueous.
 It has limited distribution in the world.
 Nonaqueous liquids may be classified as structured or
unstructured depending on the level of surfactants and other
component.
 Nonaqueous detergents can contain all the primary formulation
components, including those that are not compatible with or
difficult to formulate in aqueous systems.
157

Physical Characteristics of HDLD
 The physical form and appearance of laundry liquids can vary
greatly between different regions of the world.
 These variations in liquid types from region to region are largely
dictated by the laundry habits and personal choices of the
consumers in that particular market.
158

 Although the first major commercial heavy-duty liquid composition
was formulated with a builder system, the concentrations of
builders and surfactants it delivered into the washing solution
were lower than those provided by conventional detergent
powders.
 Antiredeposition agents, generally carbohydrate derivatives such
as carboxymethylcellulose (CMC), had been introduced into
laundry powders to prevent graying after a number of repeat
wash cycles.
159

Performance and Environment !
 The popularity of heavy-duty liquids for pre treating stains was
thus based not only on convenience but also on real performance.
 To overcome biodegradability then use different straight chain
raw materials such as LAS.
 Restrictions on the use of phosphate derivatives in laundry
detergents.
 This was replaces by NTA (trisodium nitrilotriacetate) a powerful
builder compared to condensed phosphate in its efficiency in
sequestering calcium ions.
 It was then replaced by sodium citrate!!! Less powerful.
160

Polymers Use in Light Duty Liquid Detergent
Used to give various benefits.
 For example, polyoxyethylene diamine is used to increase grease
cleaning,
 Polyacrylate to aggregate and suspend particles,
 Amino acid copolymer to tackle resistant soiling.
 Polyethylene glycol to increase solubility.
 Ethylene oxide–propylene oxide copolymer to increase solubility,
grease cleaning, or foam stability, or to improve mildness.
 Different colors and fragrance to enhance cleaning.
 Spring Sensation!!! Colgate - Palmolive
161

Personal Cleaning Products
 Include bar soaps, gels, liquid soaps and heavy duty hand
cleaners.
 These products get their cleaning action from soap, other
surfactants or a combination of the two. The choice of cleaning
agent helps determine the product's lathering characteristics, feel
on the skin and rinsability.
Bar soaps or gels are formulated for cleaning the hands, face and
body.
162

Personal Cleaning Products
 Depending on the other ingredients, they may also moisturize the
skin and/or kill or inhibit bacteria that can cause odor or disease.
Specialty bars include transparent/translucent ‫نصف‬
‫شفاف‬ soaps,
luxury soaps and medicated soaps.
 Liquid soaps are formulated for cleaning the hands or body, and
feature skin conditioners. Some contain antimicrobial agents that
kill or inhibit bacteria that can cause odor or disease.
 Heavy duty hand cleaners are available as bars, liquids, powders
and pastes. Formulated for removing stubborn ‫عنيد‬ , greasy dirt,
they may include an abrasive.
163

Laundry Detergents and Laundry Aids
 Available as liquids, powders, gels, sticks, sprays, sheets and bars.
 They are formulated to meet a variety of soil and stain removal,
bleaching, fabric softening and conditioning, and disinfectant needs
under varying water, temperature and use conditions.
 Laundry detergents are either general purpose or light duty.
 General purpose detergents are suitable for all washable fabrics.
Liquids work best on oily soils and for retreating soils and stains.
Powders are especially effective in lifting out clay and ground-in dirt.
 Light duty detergents are used for hand or machine washing lightly
soiled items and delicate fabrics.
164

Laundry Aids
Laundry aids contribute to the effectiveness of laundry detergents
and provide special functions.
 Bleaches (chlorine and oxygen) whiten and brighten fabrics and
help remove stubborn stains. They convert soils into colorless,
soluble particles that can be removed by detergents and carried
away in the wash water.
 Liquid chlorine bleach (usually in a sodium hypochlorite solution)
can also disinfect and deodorize fabrics. Oxygen (color-safe)
bleach is more gentle and works safely on almost all washable
fabrics.
165

Laundry Aids
 Bluing contain a blue dye or pigment taken up by fabrics in the
wash or rinse. Bluing absorbs the yellow part of the light spectrum,
counteracting the natural yellowing of many fabrics.
 Boosters enhance the soil and stain removal, brightening,
buffering and water softening performance of detergents. They
are used in the wash in addition to the detergent.
 Enzyme presoaks are used for soaking items before washing to
remove difficult stains and soils. When added to the wash water,
they increase cleaning power.
166

Dishwashing Products
 Dishwashing Products include detergents for hand and machine
dishwashing as well as some specialty products. They are
available as liquids, gels, powders and solids.
1. Hand dishwashing detergents remove food soils, hold soil in
suspension and provide long-lasting suds that indicate how much
cleaning power is left in the wash water.
2. Automatic dishwasher detergents, in addition to removing food soils
and holding them in suspension, tie up hardness minerals, emulsify
grease and oil, suppress foam caused by protein soil and help
water sheet off dish surfaces. They produce little or no suds that
would interfere with the washing action of the machine
167

Dishwashing Products
3. Rinse agents are used in addition to the automatic dishwasher
detergent to lower surface tension, thus improving draining of the
water from dishes and utensils. Better draining minimizes spotting
and filming and enhances drying.
4. Film removers remove build-up of hard water film and cloudiness
from dishes and the interior of the dishwasher. They are used
instead of an automatic dishwasher detergent in a separate cycle
or together with the detergent.
5. Lime and rust removers remove deposits of lime and/or rust from
the interior of the dishwasher. They are used when no dishes or
other dishwasher products are present
168

Household Cleaners
 Available as liquids, gels, powders, solids, sheets and pads for use
on painted, plastic, metal, porcelain, glass and other surfaces, and
on washable floor coverings.
 Because no single product can provide optimum performance on
all surfaces and soils, a broad range of products has been
formulated to clean efficiently and easily. While all-purpose
cleaners are intended for more general use, others work best
under highly specialized conditions.
1. All-purpose cleaners penetrate and loosen soil, soften water and
prevent soil from re-depositing on the cleaned surface. Some also
disinfect.
170

Household Cleaners
2. Abrasive cleansers remove heavy accumulations of soil often
found in small areas. The abrasive action is provided by small
mineral or metal particles, fine steel wool, copper or nylon
particles. Some also disinfect.
3. Specialty cleaners are designed for the soil conditions found on
specific surfaces, such as glass, tile, metal, ovens, carpets and
upholstery, toilet bowls and in drains.
4. Glass cleaners loosen and dissolve oily soils found on glass, and
dry quickly without streaking.
Glass and multi-surface cleaners remove soils from a variety of
smooth surfaces. They shine surfaces without streaking.
171

Household Cleaners
5. Tub (container), tile (surface) and sink cleaners remove normal
soils found on bathroom surfaces as well as hard water deposits,
soap scum, rust stains, and/or mildew and mold. Some also treat
surfaces to retard soiling; some also disinfect.
6. Metal cleaners remove soils and polish metal ware. Tarnish, the
oxidation of metal, is the principal soil found on metal ware. Some
products also protect cleaned metal ware against rapid re-
tarnishing.
172

Household Cleaners
7. Oven cleaners remove burned-on grease and other food soils
from oven walls. These cleaners are thick so the product will cling
to vertical oven surfaces.
8. Rug shampoos and upholstery cleaners dissolve oily and
greasy soils and hold them in suspension for removal. Some also
treat surfaces to repel soil (keep away soil).
9. Toilet bowl cleaners prevent or remove stains caused by hard
water and rust deposits, and maintain a clean and pleasant-
smelling bowl. Some products also disinfect.
173

Household Cleaners
10. Drain openers unclog kitchen and bathroom drains. They work
by producing heat to melt fats, breaking them down into simpler
substances that can be rinsed away, or by oxidizing hair and
other materials. Some use bacteria to prevent grease build-up
which leads to drain clogging.
174

Household Cleaners
 Soap and detergent manufacturing consists of a broad range of
processing and packaging operations.
 The size and complexity of these operations vary from small plants
employing a few people to those hundred workers.
 Products range from large-volume types like laundry detergents
that are used on a regular basis to lower-volume specialties for
less frequent cleaning needs.
175

Shampoo and Conditioners
 Shampoos are liquid detergents designed to clean hair and scalp.
 Aesthetic properties, such as appearance (clear or pearlescent),
viscosity, and fragrance, are perhaps more important in this
product group than other products.
 Shampoos almost always contain additives with activity in areas
other than cleaning and foaming, designed to provide specific
performance attributes such as hair luster and manageability and
elimination of dandruff.
176

Shampoo Characteristics
 Mildness to skin and low irritation to eyes are therefore important
requirements for shampoos.
 Salts, generally sodium but also triethanolammonium, of long-chain
alcohol sulfates and alcohol ether sulfates are the most widely used
surfactants in shampoo formulations. Alkanolamides act as viscosity
regulators and foam stabilizers.
 The most general benefits associated with the use of conditioners are
a reduction in static charge on hair and hence a greater ease of
combing, that is, improved manageability.
 Cationic, quaternary surfactants and cationic polymers provide these
benefits as a result of electrostatic adsorption on hair.
177

 The main function of the primary surfactants in a shampoo is to
provide a cleaning beneﬁt.
 Levels of surfactant between 8 and 20 % are generally employed
in shampoos.
 Ammonium lauryl sulfate (ALS) and sodium or ammonium laureth
sulfates (SLES or ALES) are used either alone or in combination.
 Many shampoos also contain special ingredients such as vitamins,
pro-vitamins, antioxidants, and herbal and marine extracts.
178

179
Ammonium Lauryl Sulfate (ALS)
Sodium or Ammonium Laureth Sulfates (SLES or ALES)
Alpha Oleﬁn Sulfonates (AOS)
Cocodiethanol Amide (CDEA)
Cocomonoethanol Amide (CMEA)

180

Shampoo with Multiple effect
 Two-in-one” shampoos that combine cleaning and conditioning
benefits.
 They are oil in water emulsion.
 They contain other related silicones such as dimethiconol,
amodimethicone, and dimethicone copolyol.
 Many of these materials are not soluble in water, it is necessary to
incorporate these ingredients into the product with emulsifying
agents or stabilizers.
181

Shampoo with Multiple effect
 Provide cleaning, conditioning, and antidandruff benefits in one
product.
 Shampoos are also formulated with antidandruff agents. Water-
insoluble antidandruff agents, such as zinc pyrithione (ZPT),
selenium sulfide, climbazole, coal tar derivatives
182

183
Shampoo

Fabric Softeners
 Fabric softeners or conditioners are designed to deliver softness to
washed clothes and to impart a pleasant smell.
 Contains surfactants, “quats” (quaternary ammonium surfactants),
which adsorb onto fabric surfaces. Di-hard tallow
dimethylammonium chloride (DHTDMAC) has been the most
commonly used softening ingredient for several decades.
 Fabric softeners are not truly solutions?
 The long-chain quaternary salts do not dissolve to form an
isotropic solution.
184

Fabric Softeners
 Cotton is the primary target substrate for fabric softeners.
 Fortunately, the agents that confer softening to cotton fibers also
reduce the buildup of static charges on synthetics.
185

Conventional Fabric Softener Formulation
 Around 5% quaternary surfactant.
 Low concentration of levelling agents often non ionic surfactant,
assist in the uniform deposition of the softening quats.
 Buffering systems to ensure an acidic pH.
 Solvent such as isopropyl alcohol (10-15%) to ensure a suitable
viscosity.
 An additives to improve ease of ironing and to reduce wrinkling
tendedency of treated textile (silicone derivatives such as
polydimethyl siloxanes.
186

Any alternative to Quaternaries?
 Imidazolinium compounds of superior rewet performance Why?
 Because with continuing usage and buildup of cationics on the
substrate, the water absorption of the substrate can be adversely
affected.
 The use of anionic detergents in the main wash can mitigate this
phenomenon because the anionic surfactant can combine with the
cationic fabric softener to form a combination that is removed as
part of the oil on the fabric.
 Therefore do not use anionic.
187

Environmental concern of the DHTDMAC!!
 Low biodegradability.
 Replace it with esterquats. This is not a simple one to one
replacement formula. It requires a full reformulation.
188

Facial Cleanser
• Aqua/Water
• Palmitic acid
• Myristic acid
• Lauric acid
• Stearic acid
• Potassium hydroxide
• PEG-7 Glyceryl cocoate
• PEG-150 Distearate
• Glycerin
• Sodium laureth sulfosuccinate
• Limonene
• Linalool
• Zinc PCA
• Propylparaben
• Propylene glycol
• Disodium EDTA
• NaCl
Prof. Amer EL-Hamouz 191 191
Cream

Foam Stabilizer
 While there is no direct correlation between foam and cleaning,
consumers in general use foam volume and foam persistence to
judge the performance of an LDLD.
 Fatay alkanol amides:
 LMMEA (lauric/myristic monoethanol amide.
 Amine oxides:
 DMDA (dimethyldodecyl amine oxide)
192

Test Methods and Performance Evaluation
These tests use a variety of soils and washing conditions (e.g.,
temperature, time, water hardness, mechanical action or not).
The test methods discussed below are classified in five categories:
 Evaluation of cleaning performance;
 Evaluation of foam performance (volume and stability);
 Evaluation of mildness;
 Evaluation of antibacterial efficacy;
 Other tests
193

Cleaning Performance
 It is the most important characteristics of a dishwashing liquid since
consumers purchase the product for washing dishes, and their
principal expectation is the removal of greasy soils.
 Test methods for cleaning performance have mainly focused on
greasy soils.
 Baumgartner Test
 Cup test
 Hand dishwashing test (plate count)
 Static Soaking Test
 Emulsion Stability Test
194

Cleaning Performance
 Hand dishwashing tests provide the best performance
information about the entire product as they use soils and wash
conditions as close as possible to those encountered by consumers
under normal conditions.
Drawbacks:
 This type of test usually takes a long time to complete.
 Tt is subjective, and thus can vary from operator to operator.
195

Foam Performance
 Foam volume and foam mileage tests are widely used for
evaluating LDLDs.
 Foam volume tests measure the amount of foam a composition can
generate with and without soil. Foam mileage, sometimes referred
as foam stability, measures the ability of a detergent to maintain
its foam with soil present or while it is introduced.
 Foam Volume Tests (with soil or without soil)
 Foam stability test It measure a product’s ability to resist foam
depletion in the presence of soil.
 Miniplate Test
 Shell Test
196

Mildness Evaluation
 Assessments typically involve clinical and sensory evaluations of
skin irritation.
 Mildness evaluations are usually conducted in both in vivo and in
vitro testing.
In Vivo tests:
 Frosch–Kligman Soap Chamber Test.
 PatchTests.
197

Mildness Evaluation
198

Mildness Evaluation
199

Antibacterial Efficacy Evaluation
 Agar Patch
 Skin Occlusion and Bacteria Recovery Test or Cup Scrub Test.
 Hand Imprint Test. This test is a qualitative test. It assesses the
residual activity on hand products.
 Health Care Personnel Hand Wash (HCPHW).
200

Other Tests
1. Drainage test
2. Rinsing test:
 This involves making a solution of product, charging it to a
container, and stirring. The solution is discharged from bottom of
the container leaving residual foam in the container.
 Tap water is added to the container with residual foam and
stirred again.
 The stirring and draining steps are repeated until no foam
remains in the container.
 The product that needs fewer additions of water has better
rinsing properties.
201

3. Cloud/Clear tests
 The temperature at which the sample first becomes turbid is the
cloud point.
 The clear point: The temperature increases slowly until the sample
becomes clear again.
 The acceptable cloud and clear temperatures are set based on the
conditions to which the products may be subject.
 The greater the number of EO, the greater is the water solubility
and the higher is the cloud point for the same lipophile.
202

Cloud/Clear tests
 The presence of electrolyte such as sodium chloride, reduces both
cloud point and water solubility. This is due to the ions competence
for water.
203
Chemical Cloud Point, C
Ethoxylate alchohol
EO6
57
Nonylpheynol
Ethoxolate NP9 82
NP9 + 1% SODIUM
CHLORIDE 77

FORMULATION TECHNOLOGY
 Formulating an LDLD is
both a science and an
art. It requires a good
balance between product
performance, aesthetics,
safety, and cost.
 From the consumer point
of view, the important
attributes for a hand
dishwashing liquid are
listed in Table 7.9
204

Formulation Stages
Formulation of LDLDs typically involves
(1) Specify your desired performance.
(2) selecting appropriate raw materials
(3) developing formulas and optimizing for performance
(4) optimizing product aesthetics
(5) testing product safety
(6) optimizing product cost
(7) aging for product stability
(8) validating with consumers,
and (9) documenting advertising claims
205

Formulating for Effective Cleaning
 Relies on the interfacial properties provided by surfactants.
 The use of a combination of surfactants is necessary for an LDLD to
be effective against a wide spectrum of soils encountered on a
variety of surfaces in the real world.
 Significant number of patents are shown in Table 7.10.
 The technology utilized in these patents ranges from special
surfactants, surfactant mixtures, salts, and microemulsion to the use
of special additives such as lemon juice and abrasives.
206

Formulating for High and Long-Lasting Foam
 Copious foam usually requires the use of high-foaming surfactants,
typically anionic or amphoteric surfactants or a mixture of
surfactants.
 Long-lasting foam often requires the use of foam stabilizers in
addition to surfactant mixtures.
207

Formulating for Mildness
There are essentially two approaches to formulate an LDLD for
mildness:
1. Use mild surfactants such as nonionic surfactants, amphoteric
surfactants, or a combination of such surfactants;
2. Use additives that are anti-irritants such as modified protein or
polymers.
208

Formulating for Desirable Aesthetics
Color, fragrance, cloud and clear
points, viscosity, and product stability.
a) Cloud and Clear Points.
 Cloud point below 4C and the clear
point not exceed 10C.
 The cloud and clear points of an
LDLD can be adjusted using
hydrotropes such as sodium xylene
sulfonate (SXS), sodium cumene
sulfonate (SCS) and alcohols
209
Effect of SXS on clear
point of LDLD Product

Formulating for Desirable Aesthetics
b) Viscosity (typically 100-500 cP)
c) Physical stability (precipitation, phase separation, or microbial
contamination).
 Elevated temperature.
 Exposure to sunlight.
 Test pH, color, fragrance from time to time.
210

Factors Affecting Performance
1- Effect of surfactant type.
 Do better job if detergent contains mixture of surfactants of
different type and different chain length.
 Anionic with nonionic or amphotric mixture resulted in reduction of
the CMC, more grease cleaning, better foaming due to head
interaction.
211

2. Effect of carbon chain distribution
 The foam stability depends on water hardness as well.
 The location of the phenyl group on the alkyl chain (within the
limits of commercially available LAS) has little effect on the
performance.
 For SAS (secondary alkane sulphonate), anionic surfactant used,
chain length of C14-C15, more plates are cleaned.
212

213
 AEOS: alkylethoxy sulfate
 LAS: Linear alkylbenzene sulphonate.
 LMMEA: lauric/myristic monoethanol amide

3. Effect of pH
 The pH can do more than giving a stable formulation.
 Acidic pH can act as an antibacterial condition.
 Slightly acidic pH (around 5.5) is matched to the physiologic pH
of skin.
 As a balance to give maximum grease cleaning while maintaining
skin mildness, most commercial products have a pH close to neutral.
 Most surfactants are also most stable under neutral pH
214

4. Effect of Inorganic Ions
 This is very important factor in formulating dishwashing liquids.
 Present as impurities in most commercial surfactants.
 They are also present as calcium and magnesium carbonates,
sulfates, and chlorides in hard water.
 They are deliberately added to products by some manufacturers
as important performance boosters and viscosity modifiers.
 One of the effects of increased electrolyte concentration is
lowering of the CMC.
215

4. Effect of Inorganic Ions
 The most important effect of electrolytes is the effect of Ca2+ and
Mg2+ ions on dishwashing performance.
 Numerous patents deal with the beneficial effects of both ions on
dishwashing performance.
 It is thought that these divalent ions form a complex with anionic
surfactants.
 This complex allows the anionic surfactant to adsorb more readily
on surfaces with a negative surface charge.
216

5. Effect of raw materials variation.
 Some LAS mixtures appear to be self hydrotroping; others need
extra hydrotrope.
 Commercial LAS contains various amounts of the 2-phenyl isomer
and dialkyltetralin sulfonates.
 The 2-phenyl content significantly affects the solubility, and the
tetralins considerably reduce the viscosity
217

Recent Patent Trends
 Mixed surfactants to modify performance.
 Use of microemulsion technology to improve grease removal.
 Use of novel surfactants.
 Use of polymers
 Use of enzymes in hand dishwashing
 Cleaning extra tough soil.
218

Novel Surfactants
 Examples of novel anionic surfactants are mid-chain branched
ethoxy sulfates.
 The chelating surfactant ethylene diaminetriacetate is claimed to
provide good foaming and grease cutting properties particularly in
hard water.
 Look at Table 7-14
 Some novel nonionic surfactants include an
ethoxylated/propoxylated nonionic surfactant, a gemini surfactant,
and a bridged polyhydroxy fatty acid amide.
219

Polymers in LDLD’s
Polymers can interact with surfactants and provide many interesting
properties:
 Soil resistance due to amino acid copolymers.
 Grease release agent due to polyethylene glycol.
 Increased grease removal.
 Enhanced foam volume and duration
 Increased solubility, and enhanced mildness by ethylene oxide–
propylene oxide copolymers
 Look at Table 7-15.
220

Use of Enzymes in LDLDs
The enzymes are added for:
 Skin conditioning, removing protein soils (protease), removing juice
soils (pectinesterase), removing starch based soils (amylase), and fat
degrading (lipase).
 One of the suppliers is Novo Nordisk
221

Disinfectants
 One technology used to obtain disinfectant properties is the use of
acids such as salicyclic acid or alpha-hydroxy acids.
 The pH of these formulations are claimed to be between 3 and 6.
 The second type of disinfecting formulation utilizes quaternary
ammonium compounds the active antimicrobial agent.
 However, these formulations will need to avoid using common
anionic surfactants so as not to form the inactive anionic–cationic
complex.
 Other active disinfectants are Zn salts, terpene alcohols,
trichlorocarbanilide, hydrogen peroxide, and an iodophor
222

Enhanced Mildness and Skin Feel
 The use of high level nonionic surfactants formulated with the
specific purposes of increased mildness. Look at Table 7.18.
 The ingredients claimed to benefit the skin feel attributes of the
hands are an organosilane, monoalkyl phosphate ester, succinamate,
and sucroglyceride surfactant
223

Builders and Fillers
 Fillers are additives added to a detergent to cheapen the product.
 Sometimes the distinction between builders and fillers is blurred
(unclear).
 Sodium silicate and sodium carbonate which are added to
household soaps to reduce cost also have some beneficial effects.
 Sodium carbonate: in manufacture of Na salts, glass, soaps, for
washing wool, textiles, etc., in bleaching linen, cotton, general
clenser, in water softening.
 Sodium silicate: as a binder
224

Problems Facing Chemical, Soap & Detergent
Industry
 Problems Related to Facilities & Equipment
 Raw & intermediate material
 Equipment and machinery
 Sites and industrial buildings
 Energy, water , roads and communications
 Packing & wrapping
 Problems Related to Technology
 Marketing Problems
 Financial & Financing Problems
225

Soap and Detergent
Construction Model
226

Which product for
which job?
Manufacture
needs
What things to get rid
of? Identify the dirt.
How frequent you need to use it? What
is the cleaning needs? Light duty or
heavy duty?
Product category needs
PC L DW HC

Soap Detergent (included Surfactants)
Desired property
achieved by choosing
the right surfactants
See Table[1]
Foam
Anionic Best
Amphoteric Better
Nonionic Good
Cationic Poor
Mildness
Anionic Variable
Amphoteric Best
Nonionic Good
Cationic Poor
Detergency
Anionic Better
Amphoteric Good
Nonionic Good
Cationic Fair
Cleaning Type
Soap or Detergent
See Table [2] for differences
See Table [3] for ingredients
Raw materials
1- Alkali (NaOH, KOH)
2- Fats and oil

555674999-Soap-and-Detergent-Manufacturing-Course-2nd-Sem-2019.pdf

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