Cleaning Products Fundamentals Seminar Other Performance Additives: Bleaches, Enzymes, Polymers, Opt

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Cleaning Products Fundamentals SeminarOther
Performance AdditivesBleaches, Enzymes,
Polymers, Optical Brighteners, Acids, Bases and
Odor CounteractantsDr. J. ShulmanConsumer
and Industrial SpecialtiesRohm and Haas Company
CSPA Cleaning Products Fundamentals Seminar
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Performance Adjuvants(Completing the Package)

• Bleaches - Chlorine/Oxygen
• Enzymes - Protease/Amylase/Lipase/Cellulase
• Polymers - Dispersants/Dye Transfer Inhibitors/
  Soil Release Agents/Rheology Modifiers/Opacifiers
• Optical Brighteners Stilbene Derivatives (FWA)
• Acids/Bases - Organic/Inorganic
• Odor Counteractants - Baking Soda/Cyclodextrin/
  Zinc Ricinoleate

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The Fundamental Cleaning Process
SOILED SURFACE SOIL
SURFACE
Natural process Forced process
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Dissecting The Problem - Soil/Stain Types
Soils
Stains
Organic Inorganic Oxidizable
Enzymatic Greasy Particulate Perspir
ation Dust Coffee/Tea
Egg Oils
Clay Grease/Fats Clay
Wine Grass Cosmetics
Dust


Oily Films Smoke Grass
Cocoa -----Collar
Soil----- Soap Scum Insoluble
Fruits Starches

Mineral Salts Melting Point Tend
to Breaking Need to Be
Melting Point Tend to Critical for
Redeposit C - C Bonds Digested
Prior Critical for Redeposit Removal
Needed for Removal
for Removal Removal Alternative Approach
Required
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Understanding Soil/Surface Interactions
Soft Surfaces (Fabrics)
Cotton Synthetic Blends
Synthetic Rough
Very Commonly Smooth

Found High
Hydrophobic
Surface Area (Negatively Charged)
Hydrophilic Durable Press
Poor Water Finishes Absorbency
Absorbent
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Understanding Soil/Surface Interactions
Hard Surfaces
Tableware/Metallic Fixtures
Floors, Walls, etc. Ceramic
Glass, Metal, Plastics Porous
Smooth Reflecting Higher
Difficult
Higher Properties Difficult
Soil to Obtain
Soil Dependant to Obtain
Retention Spotless
Retention on Surface Spotless

Treatment
Prone to
Needs Higher
Chemical Damage Wettability (Reduce
Acidic Environment May
Interfacial Tension) Facilitate Cleaning
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Typical Levels of Performance Additives

• Additive Laundry Autodish
  Specialty
• Bleach 0-20 1-10 0-50
• (Chlorine, Oxygen)
• Enzymes 0.5-2 0-2 0-5
• (Protease, Amylase, Lipase, Cellulase)
• Polymers 1-5 0-8
  0-10
• (Dispersants, DTIs, SRPs, Rheology Modifiers)
• Brighteners 0.1-0.3 Not Used
  0-1
• (FWAs, Dye Fade Inhibitors)
• Acids/Bases 0-80
  0-50 1-80
• (Organic/Inorganic)
• Odor 0-1 0-20 0-20
• Counteractants (Baking Soda ONLY)
• (Baking Soda, Cyclodextrin, Zinc Complexes)

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Bleaches

• Bleaching Agents Have Three Main Roles
• Stain Removal
• Disinfection (Eliminate Micro-Organisms)
• Whiteness Maintenance

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Common Bleaching Agents

• Liquid Sources
• Sodium Hypochlorite - NaOCl
• Hydrogen Peroxide - H2O2
• Solid Sources HO
  O---O OH
• Metal (Na) Perborates Na B-
  B- Na
• HO
  O---O OH
• Metal (Na) Percarbonate Na2CO3 .1.5 H2O2
• Isocyanurates (Acid or Salts) Na
• 
  N
• 
  OC CO
• 
  Cl-N N-Cl
• 
  C
• 
  O

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Oxygen Bleach Mechanism

• HO O--O OH
• Na B - B - Na 2 H2O2 2 Na
  2 H2BO3-
• HO O--O OH
• H2O2 OH - H2O
  HO2-
• 
  OH - O
• 
  

H2O
(Active)
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Oxygen Bleach Activation

• O O
• CH3-C C-CH3
• N CH2 CH2
  N 2 H2O2
• CH3-C C-CH3
• O O
• TAED (tetraacetylethylene diamine)
• O
• CH3-C H
  O
• N CH2 CH2 N
  2 CH3C-OOH
• H C-CH3 Peracetic
  Acid
• O
  

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Bleaching Agents

• Hypochlorite (Chlorine)
• Effective at Low Temp.
• Decolorization of Textiles
• Promotes Fiber Damage, Corrosion of Metallic
  Surfaces
• Compatibility Issues with Enzymes, Surfactants,
  and Fragrances
• Characteristic Odor

• Perborate/Percarbonate (Oxygen - Color Safe)
• Optimal Activity at Temperatures gt60oC (Requires
  Activator to be Effective at Low Temp.)
• Less Effective on Select Soils/Stains
• Compatible with Enzymes, Detergent Actives
• Low/No Odor

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Enzymes

• Biocatalysts Used to Promote the Hydrolytic
  Cleavage of Chemical Linkages. (Resulting
  Fragments are More Water-Soluble, Facilitating
  Removal During the Wash Process).
• Function More Efficaciously When Used at Moderate
  Temperatures (lt60oC), Intermediate pH (4-10) and
  Extended Contact Times.
• Ideal for Pre-Wash Applications or Soaking.

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Enzymes

• To Alleviate Concerns About Dusting and the
  Respiratory Irritation of Plant Workers, Enzymes
  are Typically Pelletized or Prilled.
• Enzymes Are Used Extensively in Powder/Liquid
  Laundry Detergents, Pre-Treaters and Have Been
  Recently Introduced into Automatic Dishwashing
  Detergent Formulations.
• Proteases (Proteins), Amylases (Starches),
  Lipases (Saponifiable Oils/Fats) and Cellulases
  (Reduces Cotton Pilling) ALL Find Utility in
  Laundry/ADD Formulations Worldwide.

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Enzyme Mechanism
Enzymes Use a Lock and Key Mechanism to
Perform A Hydrolytical Cleavage of a Peptide or
Ester Bond.
CO-
CO
O H
H2O
H
X
(soluble)
Interface (lock key)
Protein (insoluble)
CO
CO
(soluble)
C-O-
O-H
O-H
H
H- O - H
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Enzymes
Effect of Enzyme Concentration on the Removal of
a Blood, Milk and Ink Stain (BMI) Utilizing a US
Heavy Duty Powder Detergent
Typical Wash Bath Concentration
Soak Applications
Conclusion Enzymes Most Effective at Higher
Concentrations, Longer Contact Time in the Wash
Bath
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Polymers

• Polymers (Poly Many Mer Units) Are
  Materials Composed of Repeating Units or
  Monomers.
• In Laundry/Autodish/Hard Surface Cleaner
  Applications, Short Chain or Low Molecular Weight
  Polymers (2-70K Daltons) and Long Chain/High
  Molecular Weight Polymers (gt1MM Daltons) are
  Routinely Utilized.
• Polymers Can Be Comprised of the Same Unit (i.e.
  Acrylic Acid), or be a Combination of Different
  Monomers (i.e. Acrylic/ Maleic/Acrylate Ester) at
  Varying Molar Ratios, Backbone Charge (Cationic,
  Anionic, Nonionic), Charge Density and Mw,
  Altering the Properties of the Polymer.
• Polymers Can be Linear, Branched or Coiled, and
  Can Grow in Multiple Directions Forming
  Multi-Dimensional Networks. Most Copolymers are
  Synthesized in a Random Orientation.

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Hydrophile/Lipophile Variation and Application
Area
Detergents Water Treatment Mining Aqueous
Thickeners Floor Polish Graphic Arts Hair
Fixative Resins Paper Textiles Latex
Paints Industrial Coatings Cement
Modifiers Impact Modifiers for Plastics Adhesives
Ion Exchange Resins Leather Non-aqueous
systems Oil-absorbing Latex
Hydrophilic, Water Soluble Polymers
Alkali-Soluble or Swellable Polymers
Water-Insoluble Resins and Nanoparticles (Film
Formers and Particles)
Lipophilic Polymers
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Polymers for Detergency

• Polymers Commonly Used in Detergents
• Poly(Acrylic) CH - CH2
  - CH - CH2
• 
  COOH COOH
• Acrylic/Maleic CH - CH2
  - CH - CH
• 
  COOH COOH COOH
• H2C CH2
• Poly(Vinylpyrrolidone) H2C CO
• N
• 
  CH CH2
• Carboxymethylcellulose CH2-O-R
• R CH2-COONa O
• O n

O

OH
OH
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Polymers for Detergency

• Key Functions of Polymers Having a Direct Effect
  on Detergency
• Crystal Growth Modification/Inhibition
• Dispersion and Suspension Ability
• Adsorption on Surfaces/Particles
• Clay Soil Anti-Redeposition
• Sequestration of Polyvalent Metal Ions

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Polymers(General Application in Detergents)

• Sequestration
• Food Soil Dispersancy
• Particulate Soil Dispersancy
• Antiscale/Anti-Precipitate
• Rinse/Threshold (Dilute) Polymer
• 50 100 150 200 Solids
• Rinse Aids Use
  Level
• Household Laundry (ppm Bath)
• Warewash
• Transportation Cleaners
• II Laundry Linen Rental
• Food Process Cleaners
• II Laundry Industrial
• Metal Cleaning
• Non-Phosphate Autodish

Performance Functions
Applications
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Polymers

• Polymers Can Also Bring Other Functions
• to a Detergent/Cleaner
• Rheology Modification
• Thickening (Aesthetics)/Suspendability
• Flow Properties (Pseudoplasticity)
• Processing Aid
• Improved Particle Integrity/Uniformity
• Reduce Crutcher Viscosity
• Stabilization of an Insoluble Phase (Polymeric
  Emulsifiers)
• Unitized Dose Sachets (Polyvinyl Acetate Film)
• Opacifiers (Styrene/Acrylate Copolymers)

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Optical Brighteners

• Complex Dye Molecules Which Attach to Textiles/
  Substrates and Modify the Reflection of Light.
• The Whiter White Is White Light With a High
  Blue Component (Compensating for Yellowish
  Tinges), Making the Object Appear Whiter/
  Brighter to the Human Eye.
• Although Only an Aesthetic Point, This Difference
  Is Very Important in a Consumers Mind.

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Optical Brighteners

• Optical Brighteners are Highly Conjugated (Series
  of Alternating Double Bonds). The Double Bonds
  Have Electrons in the P Orbital Which Absorb UV
  Light and Then Transform the Irradiated Light
  Into Visible, Blue Fluorescing Light.
• Fluorescent Whitening Agents Selectively Adsorb
  on Textiles in the Wash Bath (Fct. of Opt.
  Bright. Concentration, Water Temperature,
  Surfactants (Competitive Adsorption) and Fiber
  Properties).
• Require Different O/B for Natural Fibers (Cotton)
  versus Synthetics (Polyamides/Polyesters).

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Acid Cleaners

• Hard Water Scale Removers
• - Dissolve Insoluble Mineral Salts (Based
  Upon Calcium, Magnesium, Iron and
  Manganese), Limescale and Rust
• Metal/Dairy Cleaners
• Toilet Bowl Cleaners
• Tub, Tile and Sink Cleaners

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Acid Cleaners

• Organic Acids Typically Include
• - Citric, Gluconic
• - Sulphamic
• - Hydroxyacetic
• - Oxalic
• - Aryl or Alkyl Sulfonic
• Inorganic Acids Typically Include
• - Phosphoric
• - Hydrochloric
• - Sulfuric
• - Nitric

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Basic Cleaners

• Heavy Duty Laundry, II and Automatic Dishwashing
  Detergent Compositions
• Disinfectants/Bleaches (Containing Hypochlorite)
• Tub, Tile and Toilet Bowl Cleaners
• All Purpose Cleaners (APCs)
• Floor Strippers
• Oven/Drain Cleaners

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Basic Cleaners

• Organic Bases Typically Include
• - Amines
• MEA (Monoethanolamine)
• TEA (Triethanolamine)
• AMP (2-Amino-2-Methyl-1-Propanol)
• Inorganic Bases Typically Include
• - Caustic (Sodium, Potassium or Ammonium
  Hydroxide)
• - Bicarbonate (Baking Soda)/Soda Ash
• - Silicates (Meta-, Di-, RU)
• - Phosphates (Pyro, Tripoly)

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Odor Control

MASK ODOR
FRAGRANCE
DESTRUCTION OF MICRO-ORGANISMS
BIOCIDES
REDUCE ODOR BY CHEM. ABSORPTION OR BINDING
ODOR COUNTERACTANTS
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Odor Counteractants

• Activated Carbon
• Baking Soda
• Borax
• Cyclodextrins (a-cyclodextrin six member sugar
  ring, ß-cyclodextrin seven member sugar ring,
  ?-cyclodextrin eight member sugar ring)
• Zinc Ricinoleate
• Clays/Aluminosilicates
• Crown Ethers

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Odor Encapsulation by Cyclodextrin
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Zinc Ricinoleate
Removes Unpleasant Smelling Substances Such as
Smoke, Isovaleric Acid, Mercaptan, Hydrogen
Sulfide, Ammonia And Amines From The Ambient Air
or Prevents Their Emission Into the Ambient
Environment by Chemical Binding.
GAS PHASE
WATER PHASE