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