Green & Plant-Based Cleaning Productscssa.com/docs/Canadian Presentation rev May 2-2007.pdfThe Global Leader in Plant Based Chemistry •The calculation of the HLB or Hydrophilic Lipophilic

The Global Leader in Plant Based Chemistry

Green & Plant-Based

Cleaning Products

May 2007


Agenda

• Background• 3rd Party Certification Program Review• Dispelling the HLB Myth• Summary


Green Cleaners: Change is in the WindResurgence of consumer interest in

environmentally friendly products (e.g. Global Warming concerns, indoor air quality, etc)

Part of Global Wellness and Sustainability MegaTrends

Greater volatility in Petrochemical industry and “risk premium” attached to petrochemical ingredients, along with escalating cost

Widespread VOC Limits for Cleaning Products

Environmentally Preferable Purchasing Policies

Some workhorse surfactant chemistries (egNPE’s) designated “toxic” and unsafe for the environment


Green Cleaners – Niche or Mainstream?

• Consumers:– Cleaner indoor air, sustainability, “natural” or “plant-

based”, narrower price premium without sacrificing performance

• Employers (Institutional & Industrial) & Retailers:– Consumer demand, less workplace hazard risk to

employees, lower liability, reduced absenteeism, potential workplace government regulation

• Manufacturers:– More stable raw material costs, more secure supply,

reduced formulated costs, reduced hazardous ingredients (ie solvents)


Household cleaning products were responsible for nearly 10% of all toxic exposures reported to U.S. Poison Control Centers in 2000 (206,636 calls). 2/3 of these involved children under six.

According to the U.S. EPA, the air inside the typical home is on average 2-5 times more polluted than the air outside—and in extreme cases 100 times more contaminated—believed to be largely due to household cleaners and pesticides (energy efficient homes = less air turnover)

The Janitorial Products Pollution Prevention Project reports one of the leading cause of job losses are injuries associated with toxic cleaningproducts, particularly glass and toilet cleaners and degreasers.

In a 2002 U.S. Geological Survey study of contaminants in U.S. stream water, 69 percent of streams sampled contained persistent detergent metabolites, and 66 percent contained disinfectants.

The U.S. market for natural household cleaning products has grown to $100 million annually, according to natural goods retailer Seventh Generation. This represents just one percent of the total household cleaners market, but it's been growing by 18-25 percent each year for the last five years.

Some Data Points


Change is in the wind

VOC LimitsEnvironmentally Preferable PurchasingNPE not allowed under EcoLogo, Green Seal,

or DfE.


Proposed Voluntary Certification of Consumer Cleaning Products Used at Institutional and Commercial Facilities. Eligible ultra-low VOC products would have a VOC content less than or equal to 25 g/l (~2%)

South Coast Air Quality Management District’s (ACAQMD)

Bathroom and tile cleaners;Glass CleanersToilet/urinal care products;General purpose degreasers;Carpet and upholstery cleaners;Metal polish/cleaners;Floor polish wax;Floor wax stripers;General purpose cleaners; andAir fresheners.


Many state governments in the USA are requiring Environmental Preferable Purchasing of cleaning products.

These programs require no APEs and reduced VOCs.

In addition Wal-Mart and Home Depot have announced their own environmental initiatives. These large corporationshave mandated that APEs be removed from products.

In Wal-Mart products containing APEs can no longer be sold

In Home Depot products with APEs can not carry the Eco Logo.


Other than Federal, State and Local Government Environmental Purchasing Programs,The I & I Industry must also cope with

The Green Building Council and LEEDS

The U.S. Green Building Council (USGBC) is the nation’s foremost coalition of leaders from every sector of the building industry working to promote buildings that are environmentally responsible, profitable and healthy places to live and work.


Green Building Rating System™ is the nationally accepted benchmark for the design, construction, and operation of high performance green buildings.

LEED gives building owners and operators the tools they need to have an immediate and measurable impact on their buildings’ performance.

LEED promotes a whole-building approach to sustainability by recognizingperformance in five key areas of human and environmental health:

sustainable site development, water savings, energy efficiency, materials selection, and indoor environmental quality.

Leadership in Energy and Environmental Design (LEED)


The LEED Rating System for Existing Buildings addresses:

whole-building cleaning and maintenance issues including chemical use

ongoing indoor air quality

energy efficiency

water efficiency

recycling programs and facilities

exterior maintenance programs, and systems upgrades to meet green building energy, water, IAQ, and lighting performance standards


What is Green Seal?

Green seal is a non-profit organizationdevoted to environmental standard setting, product certification, and public education.

It works toward environmental sustainabilityby identifying and promoting environmentallyresponsible products, purchasing, and production

Green Seal certifies finished formulations NOTindividual raw ingredients.


Hard Surface Cleaner Requirements 1. 80% soil removal using ASTM D4488 A5 soil.

2. Undiluted product shall not be toxic to humans. Considered toxic ifOral LD50 < 2000mg/kgInhalation LC50 < 20 mg/kg

3. Must not contain any carcinogen or reproductive toxin

4. Undiluted product not corrosive to skin or eyes

5. Undiluted product shall not be a skin sensitizer

6. Undiluted product shall not be combustible, flash point >150° F

7. VOC max All purpose & bathroom cleaners 1%

8. LC50 for algae, daphnia or fish > 100 mg/kg


Hard Surface Cleaner Requirements

9. Readily biodegradable

10. Product must be a concentrate

11. Fragrance must follow the Code of Practice of the InternationalFragrance Association

12. Prohibited ingredients:Alkylphenol ethoxylatesDibutyl pthalateHeavy MetalsOzone depleting compoundsoptical brighteners



Hard Surface Cleaner Requirements 1. 75% soil removal using ASTM D4488 A5 soil.

2. Can not contain chemicals on IARC groups 1, 2A, or 2B

3. Must be non hazardous under Class DDivision 1 Subdivision A andDivision 2 Subdivision A

4. pH between 3 and 10

5. No aromatic or halogenated solvents

6. Undiluted product shall not be combustible, flash point >61° C

7. VOC max 1% at use dilution, 12% in concentrate

8. Must have ozone depleting potential of ZERO

9. Readily biodegradable


Hard Surface Cleaner Requirements10. Product must be a refillable and a concentrate

11. No Fragrance only to change odor

12. Prohibited ingredients:Alkylphenol ethoxylatesToxic Metals e.g. arsenic. cadmium. chromium, silver, lead, mercury Endocrine disruptersEthylene Glycol Monomethyl ethersPhosphatesEDTA, NTAEndocrine disrupters

13. Product may not be in the form of an aerosol or wipe

14. Use only food grade dyes

15. Product must have limited effect on aquatic life


EcoLogo™ announced it is streamlining the audit for products containing surfactants listed in CleanGredients™.

CleanGredients™ is a database administered by GreenBlue.

NSF provides third party certification for all listed ingredients


What is Design for the EnvironmentThe United States EPA in conjunction with GreenBlue and NSF have designed a data base of “preferred” raw materialsIf all ingredients used to make a product are on the database it will immediately be certified as meeting the requirements for DfE.EPA Grants DfE certificationGreenBlue Developed criteria and administers the

CleanGredient databaseNSF Third party contracted to determine if a material

meets the criteria established to be listed onCleanGredient database


The Growing Environmental Awareness and Restrictions

imposed by EcoLogo or Green Seal Guidelines

Require a change in Formulations


Some manufactures of cleaning products see these changesas an inconvenience. Others as an opportunity.

Which are you???


It has been said that NPE/OPE can be replaced in a formulation simply by choosing a linear alcohol ethoxylate with the same HLB and cloud point.

This is a very simplistic approach that may produce a formulation that does not have the same performance.

It also does not address the performance deficit that can occur when VOCs in the form of solvents such as glycol ethers can only be used at very low levels in a formulation.

Lets look at why this is true

Dispelling the HLB Myth


•The calculation of the HLB or Hydrophilic Lipophilic Balance of a Surfactant was developed for surfactants whose hydrophilic portion was ethylene oxide.•When the hydrophilic portion contains propylene oxide or sugar, the calculation may not be accurate. •When this calculation is used to determine the HLB of a surfactant containing both EO and PO the result can be very misleading.

CH3(CH2)nCH2(OCH2CH2)x(OCHCH2)yOHCH3

CH3(CH2)nCH2(OCH2CH2)xOH


Griffin's method for non-ionic surfactants as described in 1954 works as follows:

HLB = 20 * Mh / M

where Mh is the molecular mass of the hydrophilic portion of the Molecule, and M is the molecular mass of the whole molecule giving a result on an arbitrary scale of 0 to 20.

•HLB = 0 corresponds to a completely hydrophobic molecule•HLB = 20 corresponds to a molecule made up completely of

hydrophilic components.

A molecule with 12 carbons and 7 moles of EO would have a calculated HLB

(325 ÷518) 20 = (0.6274) 20 = 12.5

Griffin’s Method for HLB


The Calculated HLB of a surfactant having a hydrophobe derived from a C10-C16 Fatty Alcohol with 3 moles of EO and 6 moles of PO is 4.38.

This HLB indicates that the surfactant is not water soluble, when in fact it is soluble in water at a temperature of 50°F.

The observed behavior of this surfactant indicates an HLB of about 8.

Example Where Griffin’s Method for HLB Fails


354045505560657075

Surfactant A Surfactant B Surfactant C

Surfactant A 13.0Surfactant B 12.5Surfactant C 12.8

Similar HLB Different Performance ProfileASTM D4488, A6 soil, 20° C


Usually a hard surface cleaner formulation is made up ofa surfactant, a solvent and a builder.

The question can be asked,

“How do these components Effect the HLB?”


Marzall has determined that the presence of an alcohol, glycol or glycol ether changes the effective HLB of a surfactant or surfactant mixture.

Marzell has stated….. The change of the effective HLB of anonionic surfactant depends on the amounts and hydrophobicity of the studied additive.

From this is may be concluded that the HLB of a surfactant only cannot accurately predict the performance of a formulated product containing both solvent and surfactant.


Another failure of the HLB system is that it fails to make allowance for temperature effects. With increasing temperature, the hydration of lyophilic groups decreases and the product becomes less hydrophilic i.e. the HLB decreases

Will this adversely effect your cleaning product if an employee uses hot water for a product dilution thinking to getImproved performance?


While HLB can be an important consideration whenchoosing an ethoxylated surfactant or surfactant system for emulsification. It is not an effective tool when formulating with a surfactant whose hydrophilic nature is not only based on EO.

Since the HLB of a surfactant or surfactant system changes in the presence of solvent, HLB fails to predict performancein a solvent containing system.


Why is Cloud Point Important?


Nonionic surfactants, are subject to a formation of a surfactant-rich phase usually at an elevated temperature called the cloud point.

The cloud point then, is the temperature at which a surfactant becomes insoluble in water as the sample is warmed.

Above the cloud point a surfactant ceases to perform some or all of its normal functions as a surfactant


Cloud point increases with the relative EO content anddecreases with increasing Alkyl carbon chain length

A nonionic with a 10 carbon chain and 5 EO will have a highercloud point than a nonionic with a 14 carbon chain and 5 EO

A nonionic with a 10 carbon chain and 10 EO will have a higher cloud point than a nonionic with a 10 carbon chain and 5 EO

Cloud point can be decreased in the presence of F- , OH-, Cl-, SO4, PO4, and NH4These are found in most builders

Cloud Point can be increased by the addition of large polarizable anions and some polyvalent cations e.g. H+, Li+


Cloud Point is often Concentration Dependent.

Cloud point vs. Concentration

y = 80.646x0.1369

R2 = 0.9855

50.0

60.0

70.0

80.0

90.0

100.0

110.0

120.0

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0

% active Dehypound Advanced

CP,

°F

Surfactant Concentration


The cloud point of a formulation is not the same as the cloud point of a ethoxylated single surfactant.

Alkyl Glycoside nonionic surfactants do not have a cloud point.

When formulated with a LAE or APE they will increase the cloudpoint of the formulation. Other surfactants such as betaines and octyl sulfates as well as hydrotropes such as SXS and urea can increase the cloud point of formulations.

The presence of Builders in a formulation tend to decrease thecloud point as many surfactants are less soluble in the presence of electrolytes.


An effective cleaning formulation can not be determined using HLB and cloud point.


It is a generally accepted principle that the use of two or more surfactants in a formulation will produce a product that will have an improved cleaning Performance over a single surfactant formulation.

0

10

20

30

40

50

60

70

80

Product A Product A +B Product A +C A+B+C

% Soil Removal


6062646668707274767880

1% NP-9 3% NP9 1% LAE-6EO 3% LAE-6EO CommercialProduct

Primary Cleaning ASTM D4488, A6 soilNo Builder and No Solvent

% Soil Removal

Surfactant alone is NOT Effective


Performance of 1% LAE with Glycol EtherASTM D4488, A6 soil

40

45

50

55

60

65

70

75

80

0% EB 1% EB 2% EB 3% EB 4% EB CommercialProduct

% Soil Removal


If LAE and a low level of Glycol Ether fails to make aneffective Hard Surface Cleaner, what will work??

One old chemistry has been the use of a nonionic and cationic surfactant combination; however, many cationicsare not biodegradable.


Today there are several different types of nonionics that can be used to formulate Hard Surface Cleaners

Alkyl GlycosidesAmidesEthoxylated Fatty AlcoholsEthoxylated Fatty AminesEthoxylated and Propoxylated Fatty AlcoholsEthoxylated Fatty alcohols with an End CapsHydroxy Mixed Ethers


Can an effective Cleaner be formulated using only a combination of surfactants??

YES


Performance PropertiesPrimary Cleaning @ 1% active, ASTM D4488, A6 soil.

626466687072747678

AdvancedSurfactant Blend

NP-9 LAE 91-6

% Soil Removal

Superior cleaningSuperior cleaning


Performance PropertiesSurfactant Blend vs. Consumer RTU APCs / Primary

Cleaning. ASTM D4488, A6 soil.

ASTM D4488, A6 soilASTM D4488, A6 soil

626466687072747678

Product JF Product CF AdvancedSurfactant Blend

% Soil Removal

No solvent, no builder, easy !

No solvent, no builder, easy !


US Market Product EB

US Market Product MC

US Market Product JF

Advanced Surfactant Blend(10 mL): 73,0%RL US Market Product LY

Advanced Surfactant Blend(20 mL): 79,8%RL

US Market Product CF

ADVANCED Surfactant BlendADVANCED Surfactant Blend vs. BenchmarksActual Robot-Washed Test Strips


ConcentratesConcentrates RTURTU

30.0

40.0

50.0

60.0

70.0

80.0

90.0

0.0 0.5 1.0 1.5 2.0 2.5

% non-volatile

% S

R

ADVANCED Surfactant BlendADVANCED Surfactant Blend

Product SEProduct MCProduct JDProduct SGProduct 1Product 2Water

ConcentratesConcentrates RTURTU

Performance PropertiesAdvanced Surfactant Blend vs. US Benchmarks

% Soil Removal at Use Concentration

ASTM D4488, A6 soil


505560657075808590

1% actAdvancedSurfactant

Blend

1% actAdvancedSurfactantBlend + EB

0.5% actAdvancedSurfactant

Blend

0.5% actAdvancedSurfactantBlend+ EB

% Soil Removal

Advanced Surfactant Blend + 3.9% Ethylene Glycol n Butyl Ether (Primary Cleaning. ASTM D4488, A6 soil)


Performance PropertiesAdvanced Surfactant Blend vs. NP - 9 and LAE 91-6.

Self Foam Behavior, Foam Cell. 0.1% active. 25 °C

0

200

400

600

800

1000

1200

1400

1600

1800

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0time, min.

Foam

Vol

ume,

mL

Dehypound Advanced

NP - 9

LAE 91-6

Advanced Surfactant Blend


1. HLB was developed for surfactants whose hydrophilic nature isonly from EO.

2. Calculated HLB of surfactants with other hydrophilic groupsmay not be accurate.

3. HLB is influenced by the presence of both solvents and builders

4. HLB, while a good indicator for formulating a stable emulsiondoes not predict cleaning performance.

Summary


Summary

5. Cloud Point is influenced by other surfactants, solvent, andbuilders in the formulation

6. Cloud Point is often concentration dependent being lower atlower concentrations making it difficult to formulate a concentrate that is still clear when diluted.

7. Above the Cloud Point surfactants lose some or all of their properties.


Summary

8. Alcohol Ethoxylates alone are not effective hard surface cleaners

9. Solvents increase the cleaning performance of Linear Alcohol Ethoxylates.

10. It is possible to formulate an effective cleaner using onlysurfactants without the use of solvents.

Documents

Green & Plant-Based Cleaning Productscssa.com/docs/Canadian Presentation rev May 2-2007.pdfThe Global Leader in Plant Based Chemistry •The calculation of the HLB or Hydrophilic Lipophilic