GRANULAR DETERGENT TECHNOLOGY

Tiffany Hensman
Newcastle Technical Centre
Ext 2873
Origins of Laundry Detergent Industry

Soap made by the Sumerians ~ 2500 BC

Urine used as Detergent (Ammonium Carbonate)
~ 50 AD
First Commercial Detergent - 1878
P&G launch ‘Tide’ in USA - 1946
P&G introduce first detergent containing
enzymes - 1967
P&G Laundry Detergents Today

Laundry detergent industry comprises Granules, Liquids and more

recently Tablets.

Granular detergents are split broadly into High Suds (for hand
washing and twin tubs) and Low Suds (for automatic washing
machines).

High Suds sold primarily in Asia, South America, Middle East and
Africa. Low suds sold in Europe, Japan, North America and also
some in South America, Middle East and Africa.

Currently around 130 different P&G granular formulations sold

globally (not including perfume variants) amounting to
approximately 4 million tonnes per year. Total laundry detergent
industry including liquids is over 5 million tonnes per year.
Main Groups of Detergent Ingredients

Surfactants
Builders
Polymers
Bleach
Chelants
Enzymes
Others
SURFACTANTS
SURFACTANTS
Surfactants
Builders
Polymers
Bleach
Chelants
Enzymes
Others
Surfactants Definition

A surfactant, or surface-active agent, is a substance which lowers the interfacial

tension between two phases, leading to removal of soil from fabric and foam
generation.
Surfactants are composed of a hydrophilic head and a hydrophobic tail :

Hydrophobic Group

Hydrophilic Head

Surfactants are the workhorses of the detergent formulations.

In heavy duty detergents, they play a key role in stain removal and soil suspension.
Key Anionic Surfactants: AS

Alkyl Sulphate (AS) CH3(CH2)nCH2OSO3¯

Linear : e.g. C245AS (mixed C12/C14/C15 chain lengths)

FAS (TAS) C16/18 (tallow) chain length

H3C O
-
O S O
O
Branched : HSAS
CH3 CH3 CH3
H3C
O
-
O S O
H3C
O

Can be of vegetal (coconut, palm, palm kernel), animal (tallow) or

synthetic origin (oil).
Key Anionic Surfactants: AES

Alkyl Ether Sulphates (AES)

H3C O( O
O
(CH2)m O) -
n O S O
O

- C25AE3S most commonly used in HDGs (mixed C12/C15 chain length,

three degrees of ethoxylation).

- Not very hardness sensitive as more hydrophilic, therefore used to

improve robustness against hardness.

- High foaming and very mild

Key Anionic Surfactants: LAS

Linear Alkyl Benzene Sulphonate

-
SO 3

- Excellent anionic surfactant of synthetic origin only.

- Chain length typically 11.5
- Biodegradable only under aerobic conditions
- Cheap
- Is now coming back in many HDG formulations, after its temporary removal
because of environmentalists’ pressure.
- Synthesis usually by Friedel - Crafts alkylation to produce Linear Alkyl Benzene
(LAB),which is then sulphonated.
Key Anionic Surfactants: Soap

Soaps

OH

- Total carbon number in the alkyl chain 16 - 18 for HDGs

- Widely used since historical times (of natural origin)
- Very hardness sensitive
- Mainly used as suds suppressors now.
Anionic Process

Anionic is delivered either via blown powder or via

surfactant agglomerates (ASLAS, ASAG, PULSAG).

Low levels sometimes added to other particles to improve

particle characteristics (e.g. AE3S in POZAG, FAS in
GD-Base I).

Blown powder is the primary route for anionic delivery in

Regular (big box) powders. Compact powders and tablets
use the denser, more active agglomerates.
Key Nonionic Surfactants: AEx

Alcohol Ethoxylates

H3C O( O
(CH2)m O)
n
OH

- Common nonionics used in HDGs are C24E5 and C45E7

- Excellent greasy removers, particularly the more hydrophobic greases.

- Synthesis by ethoxylation of fatty alcohols (with ethylene oxide)

Nonionic Process

Being generally more hydrophobic than anionic

surfactant, nonionics are trickier to process in a soluble
way.

Cannot put nonionic in blown powder due to

safety/environmental reasons.

Usually spray molten nonionic onto granules - levels

limited due to solubility and stickiness. Zeolite dusting
helps counteract stickiness.

Tablets use an AE7 nonionic agglomerate called NIPAG.

Good solubility due to relatively low nonionic active
level and high levels of the very soluble acetate salt.
Key Cationic Surfactants: K1 & KDB

Quaternary Ammonium Compounds

CH3
H3C + OH
N
CH3 Cl-

KDB-Base has C12-14 chain length, K1 has C8-10 chain length. K1 preferred
as readily biodegradable.
Surfactant in its own right, but also improves cleaning by increasing interfacial
packing of anionic and nonionic surfactants. Specific benefits on blood and
bacteria.
Increases hardness tolerance of surfactant system.
Also used as a fabric softening agent.
K1 and KDB-Base can either be added via blown powder (as in 2-in-1
detergents) or as a particle.
BUILDERS
Surfactants
Builders
Polymers
Bleach
Chelants
Enzymes
Others
Builder Definition

Builders are materials that can bind multivalent cations in

hard water (mainly calcium Ca2+, and magnesium Mg2+),
resulting in water softening. This enables the surfactant system
to work more efficiently via:

Reducing/preventing anionic precipitation

Inhibiting insoluble soil-Ca complexes
Preventing soil redeposition
Removing Ca and Mg ions from between clay platelets
making particulate stains easier to remove
Key Builders: STPP

- Sodium TriPolyPhosphate: Na5P3O10

- Sequestring builder (holds cations in soluble complex)
- Environmental concern has led to replacement by zeolite
in many detergents formulations, especially in Western
Europe.
O O

O- P
P
-O O O O-

O-
P O-

O
Key Builders: Zeolite

- Sodium Aluminosilicate, also called AC-Base

(AlO2)12(Na2O)6(SiO2)12.yH2O,
- Ion exchange builder (replaces Na+ ions with Ca2+).
- 3D network of aluminate and silicate tetrahedrons
channels,
- Structure :
Key Builders: Citrate

Citric acid, C6O7H8, and sodium citrate, C6O7Na3H5.

Fast binding, soluble builder. Low binding capacity

therefore usually used as a complimentary builder.

Citric acid is also used as a dispensing aid.

Key Builders: SKS6

- Sodium layered silicate, Na2Si2O5,

- Ion-exchanger builder
Key Builders: SKS6

Benefits :
- SKS-6 is a :
+ builder,
+ buffer,
+ enamel corrosion inhibitor,
consequently, SKS-6 is a compaction technology,
- builds magnesium strongly as well as calcium,

Negatives :
- cost,
- fabric residues (@ European conditions)
POLYMERS
Surfactants
Builders
Polymers
Bleach
Chelants
Enzymes
Others
Polymer Definition

Polymers are long chain molecules made by joining

together many small molecules called monomers.

Polymers can be natural or synthetic e.g. starch is a

natural polymer made up of glucose monomers;
polyester is a synthetic polymer made up of ethene
monomers.

Around 80% of the world’s output of organic chemicals

is used to make polymers.

We use various polymers in our detergents for several

functions.
Key Polymers: Polyacrylate/maleates

C O 2H

n n
C O 2H C O 2H

All regions have either polyacrylates or acrylate/maleate copolymers in the

key granular detergent brands.
Europe - EW-Base 70:30 AA:MA Copolymer ~70,000 Mw
US - LB-Base 100:0 AA:MA Homopolymer ~4,500 Mw
Japan - LD-Base 60:40 AA:MA Copolymer ~6,500 Mw

These are dispersant polymers which:

1) Suspend inorganic soil as a whiteness maintenance technology.
2) Remove inorganic soils (particularly clay based soils).
3) Act as a soluble builder for hardness ions.
4) Help structure blown powder and other particles.
Key Polymers: CMC

Carboxyl Methyl Cellulose

C H 2O R RO
O R
RO O
O
O R O
C H 2O R

_
R =H or C H 2 C O O

Deposits on soils and hydrophilic fabrics (mainly cotton, polycotton)

preventing redeposition of soil onto the fabric.
Help structure particles (ASLAS, CMC-TAED)
Key Polymers: SEB-Base

SEB-Base is a hydrophobic polyester:

O O O O O O
NaO 3S(CH 2CH 2O) 2 C CO CH 2CHO C C O CH 2CHO C C O CH 2CH 2OCH 2CH 2SO 3Na

R R
4 SO 3Na 1

It acts as a soil release polymer, modifying the surface of

hydrophobic fabrics to aid soil removal.
Key Polymers: Dye Transfer Inhibitors

Added via DTI agglomerate, they interact with dyes in solution to prevent
deposition on other items.
PVP - Polyvinylpyrrolidone PVNO - Polyvinylpyridine-N-Oxide

n
n
N O
N

O
PVPVI - Polyvinylpyrrolidone / Polyvinylimidazole Copolymer

N N
O

N
Key Polymers: DUB-Base

DUB-Base polymer works in partnership with AP-Base clay to provide fabric

softening through the wash (in 2-in-1 detergents)

DUB-Base - Polymer
(CH 2 C H2 O )n

AP-Base - Clay N a 0 . 33 A l1 . 67 M g 0 . 33 S i4 O 10 (O H ) 2

DUB polymer is absorbed onto the clay providing a loose flocculation which
dramatically increases the AP-Base clay deposition.

The mechanism is thought to be two-fold

1) Lubrication effect similar to talcum powder (smoothing of surface,
slipping layers of clays).
2) Protection of fibers during wash process by AP-Base.
Key Polymers: PB-Base

PB-Base is a polyethoxylated hexamethylene diamine quat:

CH3
CH3
(EO)24 N (EO)24
N
(EO)24
(EO)24
Interacts with negatively charged clays to provide outdoor soil
removal benefits.
Delivered via a 30% zeolite agglomerate or crutched. Has significant
potential as a process aid enabling us to reduce EW-Base.
BASF chosen supplier (other candidates considered; Clariant,
Witco).
Key Polymers: OD-Base Derivatives

Polyethylene imine derivatives

H 7(O )
N
O )7H
H 7(O )
N O )7H O )7H

( (
N N N
N N N
) )

H 7 (O
O )7 H )
O )7H N

H 7 (O
)
N
(
O 7)H

OD-Base currently used in High Suds formulations, will be replaced by the

more bleach stable ODP-Base next year.
Provide cleaning/whiteness benefits.
BLEACH
Surfactants
Builders
Polymers
Bleach
Chelants
Enzymes
Others
Bleach Definition

A bleach is an agent which decolourises a substrate via

oxidative/reductive attack. It alters the ability of the stain to
interact with light, and can also cleave chemical bonds to
make a stain more soluble.

In laundry we usually use a combination of bleach technologies.

Most formulations contain i) a hydrogen peroxide source
(percarbonate or perborate), ii) a bleach activator (TAED, HJ-
Base or NOBS) and iii) a photobleach (BH-Base). Not
currently used by P&G but under assessment for future
applications are bleach catalysts and bleach boosters.
Key Bleaches: Perborates

Two types of perborate currently used, PB1 (NaBO3.H2O)2 and PB4

(NaBO3.4H2O)2

OH
B OH
2N a+
O O
O O = (N a B O 3 .H 2 O ) 2

HO B
OH p e ro xid e c o m e s
fro m he re
They dissolve in water to generate hydrogen peroxide.
PB1 is more porous than PB4 therefore faster dissolving, however it tends to soak
up moisture leading to poorer product caking and dispensing under humid
conditions.
Key Bleaches: Percarbonate

Percarbonate is sodium carbonate with hydrogen peroxide trapped in

the crystal lattice. As the lattice dissolves, hydrogen percarbonate
is released into solution.
Formula is: 2NaCO3.3H2O2
High active and fast dissolving, also delivers extra alkalinity.
Stability of percarbonate in product has been an issue in the past but
new generation percarbonates are as stable as perborates.
Both percarbonate and perborate need to be transported and
processed very carefully under controlled conditions as they can
be EXPLOSIVE!! Recent explosion in supplier truck due to very
low levels of organic contamination.
Key Bleaches: TAED

TAED (Tetra Acetyl Ethylene Diamine) is a bleach activator,

reacting with the peroxide in the wash solution to generate two
molecules of peracetic acid per one molecule of TAED.
O
CH3 O
N CH3
CH3 N
O CH3
O
The peracetic acid generated is more effective at bleaching than
peroxide at lower wash temperatures.
Key Bleaches: NOBS

NOBS (Nonanoyl Oxy Benzene Sulphonate) is a hydrophobic

bleach activator, reacting with hydrogen peroxide in the wash to
produce pernonanoic acid.

S O 3-
O

O
N O BS

The hydrophobic alkyl chain on th pernonanoic acid enables targeted

bleaching of greasy soil (dingy build up, make up etc).
Cannot be used in Western Europe due to malodour at higher
temperatures and degradation of rubber washing machine
components.
Key Bleaches: HJ-Base

HJ-Base (NACA-OBS) is another hydrophobic bleach activator

specially developed for Western Europe, delivering strong
performance on greasy soil without the malodour/rubber hose
issues associated with NOBS.

O
O
N
H O -
SO3

NACA-OBS

Will be first introduced in Granules September 2001.

Key Bleaches: BH-Base

BH-Base is a photobleach designed to react with sunlight to release

singlet oxygen which bleaches damp clothes.
It is blue/green in colour which gives a desirable blue hue to white
garments. It is destroyed once it has reacted with sunlight,
preventing too much from building up on fabric.
Professional products (sold to hotels, restaurants etc) do not contain
BH-Base as most items are washed and tumble dried frequently
without sunlight, resulting in blue/green build up.
SO3-

N N
N SO3-

N Zn N

- N
SO3
N N
BH-Base

-
SO 3
CHELANTS
Surfactants
Builders
Polymers
Bleach
Chelants
Enzymes
Others
Chelant Definition

A chelant is a polyanionic species which is highly reactive towards

transition metals (e.g. Fe, Cu).

The chelant forms a water soluble complex with the metals which
come into the wash solution via the water and the laundry.

Magnesium sulphate (MgSO4) is used to stabilise the chelant until it

is ready for complexation.

Purpose of a chelant is to i) Stabilise the bleach during process and

in solution, ii) Enhance stain removal of highly coloured stains,
[and iii) Act as a crystal growth inhibitor].
Key Chelants: CW-Base

Diethylene Triamine Penta Methyl Phophonic acid

(DTPMP)

PO3 PO3

PO3 N N PO3
N

PO3
Key Chelants: ADS-Base

Ethylene Diamine Di Succinic acid (EDDS)

CH2 CH2
CH2 CH NH NH CH CH2

COOH COOH COOH COOH

Biodegradable replacement for CW-Base used in Western

Europe.
Key Chelants: HEDP

Hydroxy Ethane Dimethylene Phosphonic acid

HO

O OH
P P OH
HO OH O
Poor chelant but good crystal growth inhibitor,
preventing calcium carbonate encrustation on washing
machine parts and garments.
ENZYMES
Surfactants
Builders
Polymers
Bleach
Chelants
Enzymes
Others
Enzyme Definition

Enzymes are proteins which act as catalysts in the breakdown of specific

chemicalEbonds.
n z y m eAsC l they
a s s are
N a catalysts,
m e / T y p e very
S u low
p p l i levels
er are needed.
P ro te a s e S a v in a s e N ovo
In laundry granules we use four differentFN 3 classes
G e n e nofc oenzymes:
r
FN 4 G enencor
A lc a la s e N ovo
A m y la s e T erm a m y l N ovo
N a ta la s e (J E 1 ) N ovo
L ip a s e L ip o la s e U ltr a N ovo
C e llu la s e C are zy m e N ovo

Protease benefits on proteinaceous stains e.g. blood, grass, egg, gravy.

Amylase benefits on starchy food (sauces, desserts) and real item whiteness.
Lipolase benefits on greasy food and sebum.
Cellulase benefits on cotton depilling and colour restoration/maintenance.
Enzyme Process and Activity Units

Enzymes have a potential human safety risk of causing an allergic reaction

when inhaled (dust/aerosol). Overexposure can cause sensitisation which is
monitored via skin prick testing. Enzyme levels and exposure strictly
controlled in plants.

Enzymes can be denatured by harsh conditions (heat, humidity, bleach) and

therefore should be handled carefully. For both safety and stability reasons,
pure enzyme is made into dust free granulates for addition to granular
laundry detergent.

Activities of these granulates used to be difficult to compare as different

activity units were used by different suppliers for different enzymes (e.g.
KNPU, APU, KNU, KULU, CEVU). Now all enzyme activities are
expressed as milligram active per gram of granulate (mgActive/gm).
OTHER FORMULA INGREDIENTS
Surfactants
Builders
Polymers
Bleach
Chelants
Enzymes
Others
Aesthetics

Appearance and smell is the first impression a consumer has of the

product, and therefore very important.

Coloured carbonate speckle improves appearance, helps to hide

other off-white particles and is often perceived as being an active
ingredient (usually enzyme).

Perfume is critical for hiding base odour, and is one of the biggest
drivers for product acceptance. It is sprayed on to the finished
product, and sometimes accompanied by encapsulated perfume or
‘Accords’ to boost perfume longevity on garments.

Brightener is a fluorescent whitening agent that not only whitens

clothes, but also improves the whiteness of blown powder.
Suds Suppression

In High Suds products, lots of suds is key to consumers

perception that the product is ‘working’. In Low Suds
products, consumers still like to see suds but we need to
control them so that:
Oversudsing disasters are avoided (requiring mopping up),
Performance is not affected by reduction in mechanical action caused by drum
full of suds,
Suds are completely gone by the end of the wash; consumers do not like having
to rewash clothes.
GD-Base is used as a suds suppressor. It is a silicone compound
which spreads across the foam causing the bubbles to burst.
Soap is also used to control foam by forming insoluble
calcium salts in the rinse which break down the suds.
Alkalinity and Ionic Strength

In order for the anionic / builder / polymer systems to perform we

need to ensure that they remain ionised throughout the wash by
keeping the wash solution alkaline. Carbonate, bicarbonate and
silicate all help to maintain and control alkalinity (buffer) when
washing laundry (which is generally acidic). High alkalinity
however is detrimental to fabric colour care and increases risk of
gastro intestinal damage if swallowed (legal limits).

Sodium sulphate increases ionic strength which in theory could

affect surfactant packing, however in reality we usually see very
little difference in performance whether it is in or out. Sulphate is
therefore usually used as a filler or balancing ingredient. Compact
detergents contain very little sulphate. However, sulphate is used
as a process aid in some particles and blown powder, and can aid
product flowability.
Laundry Tablet Chemistry

The basic formulation of laundry tablets is much the same as

compact granules. However there are some specific ingredients to
aid tablet processing:
NIPAG is used as a soluble nonionic agglomerate, as spraying on
nonionic at desired level would make the tablet too sticky to
process. PULSAG is a special non-dusted anionic agglomerate
which also helps tabletting.
PEG 4000 polymer is used as a binder to stick the granules together,
it is mixed with the hydrotrope cyclohexane dimethanol (CHDM)
which improves solubility.
The tablet coating is made of a poorly soluble crystalline acid
(sebacic or adipic) mixed with a swelling polymer (nymcel or
purolite) which expands on contact with wash water to crack open
the coating.
CASE STUDIES
Case Studies

Chelant - low addition level

K1 - can we change the chain length spec?

AE7 - supply issue

Reblend