1. Highly Refined Mineral Oil Plasticisers in
Polyolefin-based Hot Melt Adhesives
Dr. Peter Kaali
ASC Spring Convention
29 April 2014, Orlando, FL

2. Outline
Introduction to mineral oils
Composition
Main properties
Types of mineral oils
Studies on mPO based HMA
Plasticiser performance comparison
Effect of oil loading
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3. Introduction to Mineral Oils
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4. Typical oil composition
Hydrocarbons
Paraffins Naphthenes Aromatics
Heteroatoms: S, N, O
+
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5. Main oil properties
General Solvent Power Related
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Viscosity
CA and CN
content
Viscosity Gravity
Constant (VGC)
Aniline Point
Pour Point
Flash Point
Viscosity Index (VI)
Volatility

6. Types of mineral oil plasticisers
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Paraffin content >50%
Naphthenic content <40%
Naphthenic content >40%
Higher Solvent Power Lower Plasticising effect
Higher Glass Transition Temperature Lower Resin reduction
Higher Density Lower Plasticiser loading
Lower Viscosity Index Higher Application temperature
Lower Pour point Higher Low temperature performance
ParaffinicNaphthenic
Property Impact
Aromatic content
is typically 0-15%

7. Comparison of main oil properties
Paraffinic oil
Naphthenic oil
Molecular weight
Viscosity
Flash point
Solvent power
Volatility
Polarity
Solvent power
Viscosity index
Flash point
Pour point
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8. Function of Oil in Adhesives
Main function
Plasticise
Modify rheology  Dissolve and
carry the polymer and the resin
Ease flow
Adjust tack, low and high temperature
properties
Maintain good cohesion
Key properties required
High compatibility with the polymer
and the resin
Low volatility
None or low colour and odour
HSE
FDA requirements
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G’
Polymer
Polymer + oil
Temp.

9. Types of adhesives using mineral oil
plasticisers
Hot melts and hot melt pressure
sensitive adhesives
Non-wovens
Tapes and labels
Water and solvent based
Flooring
Sealants
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10. Studies on mPO Based Hot Melt
Adhesives
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11. Test outline
Studies
Comparison of plasticiser performance
Effect of oil loading
Diaper construction adhesive formulation
Sample preparation
Spray coated to PE non-woven substrate, optimized spray pattern
Levels of add-on: 2, 3 and 4 grams
Analysis
Melt viscosity
T-peels to polymer
Initial at ambient temperature
Initial tested at 37oC after 4 hours conditioning
Aged for 2 weeks at 49oC and tested at ambient temperature
Shear adhesion failure temperature (SAFT)
Dynamic mechanical analysis (DMA)
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12. Formulation
Ingredients Description F1 F2 F3 F4
Polymer
Ethylene-octene
copolymer (MP:63oC)
20 20 20 20
Resin
Aliphatic hydrocarbon resin
(SP:103oC)
55 55 55 55
Oil
Nyflex 222B 20
Nyflex 223 20
Paraffinic-MWO 20
Dev. Product 20
Wax
PE Homopolymer
(DP:113oC)
5 5 5 5
Amounts in %wt
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13. Plasticisers
Properties Nyflex 222B Nyflex 223 P-MWO
Development
Product
Density, kg/dm3 0.93 0.9 0.868 0.884
Viscosity 40 °C, mm2/s 102 88 94 88
Viscosity 100 °C, mm2/s 9 8.4 11 9.5
Flash point, °C 218 220 260 226
Pour point, °C -35 -33 -12 -22
Aniline point, °C 103 101 123 113
Saybolt colour +30 +24 +30 +24
CA, % <1 2 <1 <1
CP, % 58 53 70 62
CN, % 41 45 30 38
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14. Melt Viscosity
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0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
Nyflex 222B Nyflex 223 P-MWO Dev. Product
Brookfieldviscosity(cP)
140
150
160
oC
oC
oC

15. Shear Adhesion Failure Temperature
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0
10
20
30
40
50
60
Nyflex 222B Nyflex 223 P-MWO Dev. Product
SAFT,(°C)

16. Peel Adhesion Performance
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0
50
100
150
200
250
300
Nyflex 222B Nyflex 223 P-MWO Dev. Product
Initialpeeladhesion,(grams)
2 3 4
0
50
100
150
200
250
300
Nyflex 222B Nyflex 223 P-MWO Dev. Product
Peeladhesionat37oC,(grams)
2 3 4
0
50
100
150
200
250
300
Nyflex 222B Nyflex 223 P-MWO Dev. Product
Agedpeeladhesion,(grams)
2 3
Add-on, (grams)
Add-on, (grams) Add-on, (grams)

17. Rheology
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1.00E+00
1.00E+01
1.00E+02
1.00E+03
1.00E+04
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
0
1
2
3
4
5
6
7
8
-20 0 20 40 60 80 100 120
G´,G´´,Pa
Tanδ
Temperature, oC
Nyflex 222B Nyflex 223 P-MWO Dev. Product

18. 0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
-20 -10 0 10 20 30 40 50 60 70 80
Tanδ
Temperature, oC
Nyflex 222B Nyflex 223 P-MWO Dev. Product
Glass Transition Temperature
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19. 1.00E+03
1.10E+04
2.10E+04
3.10E+04
4.10E+04
5.10E+04
6.10E+04
7.10E+04
8.10E+04
9.10E+04
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
32 33 34 35 36 37 38 39 40 41 42
G´,Pa
Tanδ
Temperature, oC
Nyflex 222B Nyflex 223 P-MWO Dev. Product
Indications for Creep Resistance
Excellent creep resistance
Good creep resistance
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20. Effect of oil loading
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21. Formulation
Ingredients Description F1 F2 F3
Polymer
Ethylene-octene copolymer
(MP:63oC)
20 20 20
Resin
Aliphatic hydrocarbon resin
(SP:103oC)
60 55 50
Oil Nyflex 222B
15
20
25
Wax
PE Homopolymer
(DP:113oC)
5 5 5
Amounts in %wt
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22. Melt Viscosity
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0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
15 20 25
Brookfieldviscosity,(cP)
Oil content, (wt%)
140
150
160
oC
oC
oC

23. Shear Adhesion Failure Temperature
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0
10
20
30
40
50
60
15 20 25
SAFT,(°C)
Oil content, (wt%)

24. Peel Adhesion Performance
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0
50
100
150
200
250
15 20 25
Initialpeeladhesion,(grams)
Oil content, (wt%)
2 3 4
0
50
100
150
200
250
300
15 20 25
Peeladhesionat37oC,(grams)
Oil content, (wt%)
2 3 4
Add-on, (grams)
0
50
100
150
200
250
15 20 25
Agepeeladhesion,(grams)
Oil content, (wt%)
2 3
Add-on, (grams)
Add-on, (grams)

25. Rheology
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0
1
2
3
4
5
6
7
8
1.00E+00
1.00E+01
1.00E+02
1.00E+03
1.00E+04
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
-20 0 20 40 60 80 100 120
Tanδ
logG´,G´´,Pa
Temperature, oC
15% 20% 25%
tanδ
G´
G´´

26. Glass Transition Temperature
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0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
-10 0 10 20 30 40 50
Tanδ
Temperature, oC
15% 20% 25%

27. Indications for Creep Resistance
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0
0.5
1
1.5
2
2.5
3
3.5
4
1.00E+03
1.00E+04
1.00E+05
1.00E+06
32 34 36 38 40 42
Tanδ
logG´,Pa
Temperature, oC
15% 20% 25%
tanδ
G´

28. Conclusions
High compatibility was observed of highly refined naphthenic oils with
mPO type adhesives
The performance of naphthenic oils are similar or better than paraffinics
SAFT was similar for both naphthenics and paraffinics
Higher wetting and modulus observed for naphthenic oils
For most of the formulations naphthenic plasticisers provide additional
value such as:
High solvency and compatibility
Very good flow properties
Improved adhesive properties
Good creep resistance
It is feasible to increase the oil content to 20-25% and decrease the
amount of tackifyer resin
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29. Nynas Group Head Office
P.O. Box 10700
SE-121 29 Stockholm
Sweden
Tel. +46-8-602 12 00
Fax +46-8-91 34 27
info@nynas.com
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