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Highly Refined Mineral Oil Plasticisers in Polyolefin-based Hot Melt Adhesives

Dr. Peter KaaliASC Spring Convention

29 April 2014, Orlando, FL

Outline

Introduction to mineral oilsCompositionMain propertiesTypes of mineral oils

Studies on mPO based HMAPlasticiser performance comparisonEffect of oil loading

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Introduction to Mineral Oils

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Typical oil composition

Hydrocarbons

Paraffins Naphthenes Aromatics

Heteroatoms: S, N, O+2014-04-294

Main oil properties

General Solvent Power Related

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Viscosity

CA and CNcontent

Viscosity GravityConstant (VGC)

Aniline Point

Pour PointFlash Point

Viscosity Index (VI)Volatility

Types of mineral oil plasticisers

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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%

Comparison of main oil properties

Paraffinic oil

Naphthenic oil

Molecular weightViscosity

Flash point

Solvent powerVolatility

PolaritySolvent power

Viscosity indexFlash pointPour point

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Function of Oil in AdhesivesMain 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

HSEFDA requirements

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G’

Polymer

Polymer + oil

Temp.

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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Studies on mPO Based Hot Melt Adhesives

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Test outlineStudies

Comparison of plasticiser performanceEffect of oil loading

Diaper construction adhesive formulation

Sample preparationSpray coated to PE non-woven substrate, optimized spray patternLevels of add-on: 2, 3 and 4 grams

AnalysisMelt viscosityT-peels to polymer

Initial at ambient temperatureInitial tested at 37oC after 4 hours conditioningAged for 2 weeks at 49oC and tested at ambient temperature

Shear adhesion failure temperature (SAFT)Dynamic mechanical analysis (DMA)

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Formulation

Ingredients Description F1 F2 F3 F4

Polymer Ethylene-octenecopolymer (MP:63oC)

20 20 20 20

Resin Aliphatic hydrocarbon resin(SP:103oC) 55 55 55 55

Oil

Nyflex 222B 20Nyflex 223 20Paraffinic-MWO 20Dev. Product 20

Wax PE Homopolymer(DP:113oC) 5 5 5 5

Amounts in %wt

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Plasticisers

Properties Nyflex 222B Nyflex 223 P-MWO Development Product

Density, kg/dm3 0.93 0.9 0.868 0.884Viscosity 40 °C, mm2/s 102 88 94 88Viscosity 100 °C, mm2/s 9 8.4 11 9.5Flash point, °C 218 220 260 226Pour point, °C -35 -33 -12 -22Aniline point, °C 103 101 123 113Saybolt colour +30 +24 +30 +24CA, % <1 2 <1 <1CP, % 58 53 70 62CN, % 41 45 30 38

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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

Bro

okfie

ld v

isco

sity

(cP)

140150160

oCoCoC

Shear Adhesion Failure Temperature

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0

10

20

30

40

50

60


SAFT

, (°C

)

Peel Adhesion Performance

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0

50

100

150

200

250

300


Initi

al p

eel a

dhes

ion,

(gra

ms)

2 3 4

0

50

100

150

200

250

300


Peel

adh

esio

n at

37o

C, (

gram

s)

2 3 4

0

50

100

150

200

250

300


Aged

pee

l adh

esio

n, (g

ram

s)

2 3Add-on, (grams)

Add-on, (grams) Add-on, (grams)

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

´´, PaTan δ

Temperature, oC


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

Tan δ

Temperature, oC


Glass Transition Temperature

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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´, PaTa

n δ

Temperature, oC


Indications for Creep Resistance

Excellent creep resistance

Good creep resistance

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Effect of oil loading

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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 222B15

2025

Wax PE Homopolymer(DP:113oC) 5 5 5

Amounts in %wt

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Melt Viscosity

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0

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

15 20 25

Bro

okfie

ld v

isco

sity

, (cP

)

Oil content, (wt%)

140150160

oCoCoC

Shear Adhesion Failure Temperature

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0

10

20

30

40

50

60

15 20 25

SAFT

, (°C

)

Oil content, (wt%)

Peel Adhesion Performance

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0

50

100

150

200

250

15 20 25

Initi

al p

eel a

dhes

ion,

(gra

ms)

Oil content, (wt%)

2 3 4

0

50

100

150

200

250

300

15 20 25Peel

adh

esio

n at

37o

C, (

gram

s)

Oil content, (wt%)

2 3 4Add-on, (grams)

0

50

100

150

200

250

15 20 25

Age

peel

adh

esio

n, (g

ram

s)

Oil content, (wt%)

2 3Add-on, (grams)

Add-on, (grams)

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

Tan δ

log

G´,

G´´,

Pa

Temperature, oC

15% 20% 25%

tanδ

G´

G´´

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

Tan δ

Temperature, oC

15% 20% 25%

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

Tan δlo

g G

´, Pa

Temperature, oC

15% 20% 25%

tanδ

G´

ConclusionsHigh compatibility was observed of highly refined naphthenic oils withmPO 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 additionalvalue such as:

High solvency and compatibilityVery good flow propertiesImproved adhesive propertiesGood creep resistance

It is feasible to increase the oil content to 20-25% and decrease theamount of tackifyer resin

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Nynas Group Head OfficeP.O. Box 10700SE-121 29 StockholmSweden

Tel. +46-8-602 12 00Fax +46-8-91 34 27

[email protected]

29

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