Dr. Peter KaaliTechnical Advisor
Additional Functionality of Mineral Oil in Hot Melt Formulations
New Polymer Application Laboratory
› Adhesives, PVC, TPE
› Formulation and sample preparation› Double sigma blade mixer› Hotmelt coater/laminator› Dumbell die cutter
› Mechanical testing› Shore A hardess tester, Tensile tester
› Thermal and rheology analysis› Rheometer, DSC/PDSC
› Others› UV and heat ageing chamber, › HPLC, GC-MS, FTIR
2
API Classification of mineral oils
Group I
Group II
Group III
Group IV
Group V
VI 80-119Sats < 90% and/or S > 0.03%
VI > 120Sats > 90% and/or S < 0.03%
Polyalphaolefins (PAO)
All other oils
Wide chemical spectrum
Narrower chemical spectrum
Specific molecule typeSynthetic oils
Naphthenic oilsAromatic oilsVegetable oils
Paraffinic oils VI 80-119
Sats > 90% and/or S < 0.03%
Types of mineral oil plasticisers used in adhesives
Paraffin content >50%Naphthenic content <40%
Naphthenic content >40%
Higher Solvent Power Lower Plasticising effectHigher Glass Transition Temperature Lower Resin reduction
Higher Density Lower Plasticiser loading
Lower Viscosity Index Higher Application temperature
Lower Pour point Higher Low temperature performance
Paraffinic Naphthenic
Property Impact
Aromatic content is typically 0-15%
4
Function of the oil in adhesives
Function:• Plasticise• Finetune adhesive and visco-elastic properties
- Dissolve and carry the polymer and the resin (modify rheology)- Adjust low and high temperature properties- Maintain good cohesion
Key requirements• High compatibility with the polymer and the resin• Highly saturated oils, very low levels of aromatics• Low volatility • None or low colour and odour• FDA requirements
- FDA(b) or FDA(c) for Hygiene and T&L
G’
Polymer
Polymer + oil
Temp.
5
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
6
Project
Mainly hydrocarbon resins are used in HM non-wovens with mPOsRosin resins are mainly not compatible with mPOs
Compatibility desired• Supply availability• Cost purpose
Investigation if mineral oil can work as compatibilizer• Resin and oil compatibility, cloud point• Resin and polymer compatibility, rheology• Peel performance of hot melt formulations with oil
Relative polarity
mPO Mineral oil Rosins
7
Mineral oil selection
Oil N-87 N-102 N-104 P-128
Density, 15 ˚Ckg/dm3 0.915 0.897 0.895 0.868
Viscosity, 40 ˚C mm2/s 108 84 100 104
CA , % 11 2 <1 <1
CN , % 39 43 45 28
CP, % 50 55 54 71
Aniline point, ˚C 87 102 104 128
Viscosity-gravityconstant 0.856 0.830 0.834 0.791
Relative polarity
8
Resin selection
Type of resin Softening point [˚C]
Ester based on tall oil rosin 98
Stabilized tall oil rosin ester 98
Stabilized gum rosin ester 98
Alpha, beta pinene based resin 105
Beta pinene based resin 115
Terpene phenolic resin 105
Stabilized pentaerythritol ester of tall oil rosin 96
Rosin ester 100-106
Hydrocarbon Resin (Compatible with mPE), used as a reference for peel tests 100
9
Cloud point test
Low cloud point indicates good compatibility
Oil and resin compatibility
Cloud point results I
11
80
90
100
110
120
130
140
150
Dis
solu
tion
tem
pera
ture
, oC
N-87 N-102 N-104 P-128
CP < 20 oC
Cloud point results II
020406080
100120140160180200
Rosin ester (MP) Rosin ester (CP)
Tem
pera
ture
, oC
12
Polymer and resin compatibility
No oil
Rheology to determine compatibility• Temperature sweep -20 ˚C to 130 ˚C
Materials F1 F2 F3 F4
Polymer mPE 30 30 30 30
Resin
Ester based on tall oil rosin 69
Gum rosin ester 69
Pentaerythirol ester 69
Terpene phenolic resin 69
Additive Antioxidant 1 1 1 1
13
Good compatibility – mPE and hydrocarbon resin
0
0.5
1
1.5
2
2.5
3
3.5
4
1.00E+00
2.00E+01
4.00E+02
8.00E+03
1.60E+05
3.20E+06
6.40E+07
-20 0 20 40 60 80 100
Stor
age
and
loss
mod
ulus
[Pa
]
Temperature [˚C]
G´ G´´ tan delta
14
Rheology results for formulations without oil
0
0.5
1
1.5
2
2.5
3
3.5
4
1.00E+00
2.00E+01
4.00E+02
8.00E+03
1.60E+05
3.20E+06
6.40E+07
-20 0 20 40 60 80 100
tan
delta
[-]
Stor
age
and
loss
mod
ulus
[Pa]
Temperature [˚C]
Gum rosin ester and mPEG' G'' tan delta
0
0.5
1
1.5
2
2.5
3
3.5
4
1.00E+00
2.00E+01
4.00E+02
8.00E+03
1.60E+05
3.20E+06
6.40E+07
-20 0 20 40 60 80 100ta
n dl
eta
[-]
Stor
age
and
loss
mod
ulus
[Pa]
Temperature [˚C]
Pentaerythirol ester and mPEG' G'' tan delta
Two Tg peaks for both resins
Incompatible with mPE
15
Rheology results for formulations without oil
0
0.5
1
1.5
2
2.5
3
3.5
4
1.00E+00
2.00E+01
4.00E+02
8.00E+03
1.60E+05
3.20E+06
6.40E+07
-20 0 20 40 60 80 100
tan
delta
[-]
Stor
age
and
loss
mod
ulus
[Pa]
Temperature [˚C]
Terpene phenolic resin and mPEG' G'' tan delta
0
0.5
1
1.5
2
2.5
3
3.5
4
1.00E+00
2.00E+01
4.00E+02
8.00E+03
1.60E+05
3.20E+06
6.40E+07
-20 0 20 40 60 80 100ta
n de
lta [-
]
Stor
age
and
loss
mod
ulus
[Pa]
Temperature [˚C]
Ester b. tall oil rosin and mPEG' G'' tan delta
16
Formulations with oil
Materials F1 F2 F3 F4 F5 F6 F7 F8 F9 F10 F11 F12
Polymer mPE 20 20 20 20 20 20 20 20 20 20 20 20
Resin
Ester b. tall oil rosin 59 59 59
Gum rosin ester 59 59 59
Pentaerythritol ester 59 59 59
Hydrocarbon resin 59 59 59
Oil
N-87 20 20 20 20
N-104 20 20 20 20
P-128 20 20 20 20
Additive Antioxidant 1 1 1 1 1 1 1 1 1 1 1 1
17
Rheology results for ester based on tall oil rosin formulations with mineral oil
Increased compatibility with all oils
Formulation with N-84 had the most unified peak
Relatively high tan delta peaks
0
0.5
1
1.5
2
2.5
3
3.5
4
1.00E-01
2.00E+00
4.00E+01
8.00E+02
1.60E+04
3.20E+05
6.40E+06
1.28E+08
-20 0 20 40 60 80 100
tan
delta
[-]
Stor
gae
and
loss
mod
ulus
[Pa]
Temperature [˚C]
Nytex 820 Nyflex 222B P-TWON-87 N-104 P-128
18
Rheology results for gum rosin ester formulations with mineral oil
Increased compatibility by adding oil in formulation
0
0.5
1
1.5
2
2.5
3
3.5
4
1.00E-01
2.00E+00
4.00E+01
8.00E+02
1.60E+04
3.20E+05
6.40E+06
1.28E+08
-20 0 20 40 60 80 100
tan
delta
[-]
Stor
age
and
loss
mod
ulus
[Pa]
Temperature [oC]
Nytex 820 Nyflex 222B P-TWON-87 N-104 P-128
19
Rheology results for pentaerythritol ester formulations with mineral oil
Formulation with N-84 has the highest tan delta peak
0
0.5
1
1.5
2
2.5
3
3.5
4
1.00E-01
2.00E+00
4.00E+01
8.00E+02
1.60E+04
3.20E+05
6.40E+06
1.28E+08
-20 0 20 40 60 80 100
tan
delta
[-]
Stor
age
and
loss
mod
ulus
Temperature [˚C]
Nytex 820 Nyflex 222B P-TWON-87 N-104 P-128
20
Peel tests
Laminated on release paper and polyester film• Adhesive film thickness 0,203 mm• Laminating temperature 180 ˚C (open to atmosphere)• Tape width 25 mm
90˚ peel on three substrates• Stainless steel• Glass• Polyethylene
180˚ peel
Rolling ball tack test
21
1
10
100
1000
10000
N-87 N-104 P-128
Peel
stre
ngth
, g /
25 m
m
Ester based on tall oil rosin
Steel Glass PE 180 deg C
Results of peel tests
1
10
100
1000
10000
N-87 N-104 P-128
Peel
stre
ngth
, g /
25 m
m
Gum rosin ester
Steel Glass PE 180 deg C
1
10
100
1000
10000
N-87 N-104 P-128
Peel
stre
ngth
, g /
25 m
m
Pentaerythritol ester resin
Steel Glass PE 180 deg C
1
10
100
1000
10000
N-104
Peel
stre
ngth
, g /
25 m
m
Hydrocarbon resin
Steel Glass PE 180 deg C
Conclusions
Improved compatibility was observed for all three resins
Formulation with the highest peel strength was observed with pentaerythritolester resin and N-84
None of the formulations had as high overall peel strength as the formulation with hydrocarbon resin
Two of the formulations had higher peel strength on glass than hydrocarbon resin formulation • (pentaerythritol ester resin and gum rosin ester with N-84 oil)
P-128 should have shown the best compatibility in the formulations according to polarity, however N-84 showed better results.• Indicates that other actions than polarity have an impact on compatibility
between mPOs and rosin resins.
23
TAKING OIL FURTHER
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