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Understanding the choice and the benefits of various antimicrobial plastic


additives

Conference Paper · November 2003

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Heinz Herbst
BASF Schweiz
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Understanding the choice
and the benefits of various
antimicrobial plastic additives
Anti-Microbials 2003
Nov. 5th – 6th, 2003
Brussels, Belgium

Heinz Herbst, Nadi Ergenc


Ciba Specialty Chemicals Corporation
www.cibasc.com

Objective:
• Antimicrobial plastics applications
• Microbial activity
• Triclosan
• Silver antimicrobials

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

1
Antimicrobial plastics applications
PP PA
Automotive / PET
Transportation
PVC LDPE PUR
Construction SAN
HDPE RUBBER
Packaging TPU
ABS UF PS
Textile & Carpet
PVC PC
PMMA
Rubber & Elastomers NBR HIPS
Composite
Leisure EPDM
UP
Silicon PAN
Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

Antimicrobials Product Profile


• tox / eco-tox profile
• registration / notification (EPA FIFRA, BPD 98/8/EC)
• compatibility to matrix / process
• heat stability at processing temperatures
• low volatility at processing and use temperatures
• light stability
• no-interaction with other additives
• availability at the surface / DURABLILITY
• high activity

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

2
Microbial activities
Staining
• intracellular pigments
• extra cellular dyestuffs
Deterioration of mechanical properties
• microbial degradation
• release of enzymes
• release of metabolites
Odor formation
• release of metabolites
Cross contamination
• proliferation of microbes / toxins
Biofilm formation
Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

Consequences

Staining
• loss of appearance
• loss of productivity
• value deterioration
• increased maintenance
• loss of image

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

3
Consequences

Deterioration of mechanical properties


• loss performance
• value deterioration
• increased maintenance
• liability

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

Consequences

Odor development
• reduced comfort
• value deterioration
• increased maintenance
• embarrassment
• loss of image
• attracts insects, rodents, ...

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

4
Consequences

Cross contamination
• loss of work force
• value deterioration
• product spoilage
• increased maintenance
• proliferation of microbes and toxins
e.g. Legionnaires disease
sick building syndrome
food poisoning

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

Consequences

Biofilm formation
• loss performance
• loss of hygienic properties
• cross contamination
• increased maintenance

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

5
Ciba® IRGAGUARD® Integrated Solution
IRGAGUARD® A
Algae

IRGAGUARD® B
Bacteria

IRGAGUARD® F
Fungi

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

Ciba® IRGAGUARD® range

IRGAGUARD® A 2000 series - Organic anti-algae

IRGAGUARD® B 1000 series - Organic anti-bacteria


4000 series - Silver Zeolite
5000 series - Silver Zeolite
6000 series - Silver Glass
7000 series - Silver Glass

IRGAGUARD® F 3000 series - Organic anti-fungi

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

6
Ciba® IRGAGUARD® B 1000

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

IRGAGUARD® B 1000

• outstanding safety record for > 40 years


• USP standard
• approved for cosmetic & health care products
• approved in US for several food contact
applications
• listed in Synoptic Document : SML 5 mg/kg food
• BPD notified
• EPA FIFRA approval

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

7
TOX profile of IRGAGUARD® B 1000

• not toxic in acute toxicity tests


• not sensitizing
• not carcinogenic
• not mutagenic
• not toxic to reproduction
• not teratogenic
• does not accumulate in organs or tissue
• biodegradable

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

NO formation of resistant bacteria


 SSC European Commission June 2002
http://europa.eu.int/comm/food/fs/sc/ssc/out269_en.pdf
 U.S. FDA confirms this conclusion reached earlier by an
independent advisory panel

 Exposure of Sink Drain Microorganisms to Triclosan


Gilbert et al. Appl. Environ. Microbiology, Sept. 2003, p. 5433 – 5442

 Triclosan is active against antibiotic resistant microorganisms

 Triclosan containing products are recommended at MRSA out brakes

 safety record for > 40 years

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

8
Odor Abatement
Effective odor reduction by IRGAGUARD B

container without
IRGAGUARD B 1110

container containing
Anti-Microbials 2003
IRGAGUARD B 1110
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

Summary: IRGAGUARD® B 1000


• outstanding safety record > 40 years experience
• Highly active organic antimicrobials
• Effective against a wide range of bacteria
• Optimum balance between substrate compatibility
and migration rates
• Provide efficacy over the entire life of the article
• Suitable for polymers where processing
temperatures are below 280° C

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

9
Silver based antimicrobials

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

Silver based antimicrobials for plastics

• Silver, colloidal Silver, Nano-Silver


• AgCl / TiO2
• Silver Ceramic
• Sodium Silver Zirconium Phosphate
• Silver Zeolite
• Silver Glass

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

10
Know how makes the difference
• Ag+-ion availability
• particle size
• light induced discoloration
• transparency / haze
• regulatory approvals
• abrasiveness
• dispersibility
• re-agglomeration
• efficacy after treatment

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

Silver-ion availability
Solubility Ag+
[g/100 ml] [g/ liter]
Ag insoluble

Ag-chloride 8.9 x 10-5 6.7 x 10-4

Ag-carbonate 3.2 x 10-3 2.5 x 10-2

Ag-nitrate 122 775


Ag-phosphate 6.5 x 10-3 5.0 x 10-2
Ag-oxide 1.3 x 10-3 1.2 x 10-2
Ag-sulfite 8.4 x 10-15 7.3 x 10-14

Efficacy at > 2 x 10-11 g/liter


Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

11
Light induced discoloration
20

Yellowness Index
15
10

0
0 500 1000 1500 2000 2500
-5
hours WOM
reference 0.100% NaAgZr-phosphate (A)
0.100% Silver Glass (A) 0.100% Silver Glass (B)
0.100% NaAgZr-phosphate (B) 0.100% Irgaguard B 5000
0.100% Irgaguard B 7000

weathering: HDPE plaques


WOM Ci 65 dry
Anti-Microbials 2003
Brussels, 5 - 6.11. 2003 ASTM G 26
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

Antimicrobial Efficacy in PET Fiber

Growth inhibition test according to JIS L 1902


Staphylococcus
aureus ATCC

after finishing 200


> 99.99 % reduction
6538

50x washing 200


1.00E+07

1.00E+00 1.00E+02 1.00E+04 1.00E+06 1.00E+08


Colony forming units

control 3 % IRGAGUARD B 7620


3 % IRGAGUARD B 7620

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

12
Summary: Silver antimicrobials

• common active principle = Silver+ ion


• differentiation by
• Silver+-ion availability
• processing properties
• ancillary properties
• especially useful for
• high processing and service temperatures
• thin sections
• hygienic surfaces

Anti-Microbials 2003
Brussels, 5 - 6.11. 2003
Heinz Herbst Copyright © 2003 Ciba Specialty Chemicals Inc.

13
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