Stabilization of Hot Melt Adhesives Novel Aspects

Dietmar Mder, Gerrit Knobloch Ciba Specialty Chemicals Inc.

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promoting the Interest of the Self Adhesive Tape Industry

Overview
Benefits

of antioxidants Stabilization of adhesive raw materials Stabilization of SBC hot melts PSAs for high-temperature applications Stabilization of PU-HMA Summary

promoting the Interest of the Self Adhesive Tape Industry

Benefits of Antioxidants

Antioxidants will improve properties like ..

Color stability Viscosity retention (Processing)

Prevention of skin formation (Processing) Tack retention

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promoting the Interest of the Self Adhesive Tape Industry

Overview
Benefits

of antioxidants Stabilization of adhesive raw materials Stabilization of SBC hot melts PSAs for high-temperature applications Stabilization of PU-HMA Summary

promoting the Interest of the Self Adhesive Tape Industry

Tackifier - Ageing & Testing

Low-temperature

aging simulates storage

stability (40 C)
Color Hydroperoxide Content Melt Viscosity
High-temperature

aging simulates adhesive compounding step (170 - 200 C)

Color Skinning Melt Viscosity
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promoting the Interest of the Self Adhesive Tape Industry

Tackifier - Rosin Ester

Irganox

565 prevents effectively the formation of hydroperoxides in rosin esters

Hydroperoxide Formation after aging at 40o C

HYDROPEROXIDE CONTENT (mMol/g) 0.25

ROSIN AGED IN POWDER FORM (PARTICLE SIZE 0.1-0.8 mm)

0.2

UNSTABILIZED
0.15

0.2% IRGANOX 1010 0.2% IRGANOX 565

0.1

0.05

0 0 3 6 9 DAYS 12 15 18

promoting the Interest of the Self Adhesive Tape Industry

Tackifier - Rosin Ester

Irganox

565 provides good color stability due to prevention of hydroperoxide formation

Gardner Color after aging at 40o C

GARDNER COLOR* (10min/170C) 14

ROSIN AGED IN POWDER FORM (PARTICLE SIZE 0.1-0.8 mm)

12

UNSTABILIZED 0.2% IRGANOX 1010

10

0.2% IRGANOX 565

6 0 3 6 9 DAYS 12 15 18

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* After hydroperoxide decomposition @ 170C / 10min

promoting the Interest of the Self Adhesive Tape Industry

Tackifier - Rosin Ester

Reduction

of hydroperoxides in pre-oxidized rosin ester (CH2Cl2) at ambient temperature

CONTROL Irganox 1076

Hydroperoxide Content (mMol/g)

0.1 0.08 0.06 0.04 0.02 0

0 12 24 36 Time (hours) 48 60 72

Irganox PS 800 Irganox 1726

Additive content: 5 wt%

promoting the Interest of the Self Adhesive Tape Industry

Mode of Action - Storage Stab.

Reduction

of hydroperoxides (intramolecular catalysis)

H R' S O O H O
C12H25 H3C

O O H O
H3C

R' S

C12H25

Alkyl-(2-hydroxybenzyl)-thioether
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promoting the Interest of the Self Adhesive Tape Industry

Tackifier - Hydrog. DCPD

Irganox

1726 provides good color stability in DCPD (170 C)

Yellowness Index after Ageing at 170 C 120 100 80 60 40 20 0 CONTROL 0.5% BHT 0.1% Irganox 1010 0.1% Irganox 1726

12

24

36

48

60

Ageing at 170 C (hours)

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Yellowness Index of 2 mm Plaques after Oven aging at 170 C

promoting the Interest of the Self Adhesive Tape Industry

Mode of Action - Melt Mixing

Possible

reaction mechanism: scavenging of peroxy radicals followed by -cage in reduction

POO

.
OH

+ P' H

P'

POOH S R

Crosslinking or formation of POO

High temperature: immediate decomposition PO + OH

..

HOOP S R

Reaction with polymer

cage

"In-Cage Reduktion"

.
S O R + POH

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promoting the Interest of the Self Adhesive Tape Industry

Summary I - Raw Materials

Irganox

565 provides excellent storage stability in rosin esters

excellent oxidative stability good color stability

Irganox

1726 is an efficient antioxidant for tackifier resins

good storage stability stability under adhesive mixing conditions

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promoting the Interest of the Self Adhesive Tape Industry

Overview
Benefits

of antioxidants Stabilization of adhesive raw materials Stabilization of SBC hot melts PSAs for high-temperature applications Stabilization of PU-HMA Summary

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promoting the Interest of the Self Adhesive Tape Industry

SIS-HMA - Color Stability

Irganox

1726 provides excellent color stability in SIS hot melt adhesives

Control

Irganox 1010

Irganox 1726
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promoting the Interest of the Self Adhesive Tape Industry

SIS-HMA - Initial Viscosity

Irganox

1726 provides outstanding viscosity retention upon mixing of SIS hot melts
100p SIS / 120p HC Resins / 25p Oil

Melt Viscosity after Mixing (mPa.s)

60'000 50'000 40'000 30'000

CONTROL 1.0% Irganox 1010 1.0% Irganox B225 0.25% Irganox 1726

20'000

0.5% Irganox 1726

10'000

1.0% Irganox 1726

0
0

Melt Viscosity of Control prepared in Solution: 52.400 mPa.s

HMA were prepared in a sigma blade kneader at 170C / 1h

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promoting the Interest of the Self Adhesive Tape Industry

SIS-HMA - Viscosity Stability

Irganox

1726 provides excellent viscosity stab. It also effectively suppresses skin formation
100p SIS / 120p HC Resins / 25p Oil
Melt Viscosity after Ageing at 170 C (mPa.s)
60'000 50'000 40'000 30'000 20'000 10'000 0
CONTROL 1.0% Irganox 1010 1.0% Irganox B225 0.25% Irganox 1726 0.5% Irganox 1726 1.0% Irganox 1726

Initial

12 hrs

36 hrs

48 hrs

Melt Viscosity of Control prepared in Solution: 52.400 mPa.s

HMA were prepared in a sigma blade kneader at 170C / 1h

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promoting the Interest of the Self Adhesive Tape Industry

SBS-HMA - Color Stability

Irganox

1726 provides excellent color stability in SBS hot melts (72 hrs, 170 C)

25p SBS / 48p Mixed Resins / 12p Oil

Gardner Color after Ageing (72 hrs at 170C)
12 10 8 6 4 2 0
Skin Formation

Irganox 1010 Irganox HP 2225 Irganox XP 420 Irganox XP 620 Irganox 1726
Additive content: 0.5 wt%
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promoting the Interest of the Self Adhesive Tape Industry

SBS-HMA - Color Stability

Irganox

1726 provides excellent color stability in SBS hot melts (72 hrs, 170 C)

Irganox 1010

Irganox HP2225 Irganox XP420

Irganox 1726
Irganox XP620
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promoting the Interest of the Self Adhesive Tape Industry

SBS-HMA - Viscosity Stability

Irganox

1726 provides excellent viscosity retention in SBS hot melt adhesives

25p SBS / 48p Mixed Resins / 12p Oil

Melt Viscosity at 170 C (mPa.s)

6'000

Irganox 1010
5'000 4'000 3'000
Skin Formation

Irganox HP 2225 Irganox XP 420 Irganox XP 620 Irganox 1726

48 60 72

2'000
0 12 24 36
Melt Viscosity of Control prepared in Solution: 5.600 mPa.s
HMA were prepared in a sigma blade kneader at 170C / 1h

Additive content: 0.5 wt%

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promoting the Interest of the Self Adhesive Tape Industry

SEBS-HMA - Color Stability

Irganox

HP 2225 provides excellent color retention in SEBS hot melt adhesives

30p SEBS / 100p Hydrogenated HC-Resin / 20p Oil

Gardner Color after Ageing (72 hrs at 170C)
14 12 10 8 6 4 2

CONTROL Irganox 1010 Irganox B 225 Irganox HP 2225 Irganox 1010 + Irganox PS 800 (1:1)
Additive content: 0.5 wt%
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promoting the Interest of the Self Adhesive Tape Industry

SEBS-HMA - Color Stability

Irganox

HP 2225 provides excellent color retention in SEBS hot melt adhesives (36 hrs, 170 C)

CONTROL

Irganox 1010

Irganox HP2225

Irganox XP620

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promoting the Interest of the Self Adhesive Tape Industry

SEBS-HMA - Viscosity Stability

Irganox

HP 2225 provides excellent viscosity retention in SEBS hot melt adhesives

30p SEBS / 100p Hydrogenated HC-Resin / 20p Oil
Skin Formation

Melt Viscosity at 170 C (mPa.s)

16'000 14'000 12'000 10'000 8'000 6'000 4'000

0 24

CONTROL Irganox 1010 Irganox B 225 Irganox HP 2225

48 72 96

Additive content: 0.5 wt%

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promoting the Interest of the Self Adhesive Tape Industry

PSA - Tack Retention (125 C)

Irganox

1726 provides good tack retention at elevated temperature

SIS/SBS - PSA, non-laminated
Initial Value 3 days 7 days 15 days 21 days

10'000

Polyken Tack (g) after Ageing at 125 C

1'000

100

10

0.5% Irganox 565

1.0% 2.0% 1.0% 2.0% Irganox 1010 Irganox 1010 Irganox 1726 Irganox 1726

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promoting the Interest of the Self Adhesive Tape Industry

Overview
Benefits

of antioxidants Stabilization of adhesive raw materials Stabilization of SBC hot melts PSAs for high-temperature applications Stabilization of PU-HMA Summary

24

promoting the Interest of the Self Adhesive Tape Industry

PU-HMA - Color Stability

Irganox

1726 provides excellent color stability in PUR hot melts (6 hrs, 130 C)

100

Yellowness Index 6 hrs Ageing at 130 C

80 60 40 20 0
CONTROL 0.5% Irganox 245 0.5% Irganox 1726

AO were added to the HMA at 90 C Oven ageing at 130 C in alu dishes in recirculating air oven
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promoting the Interest of the Self Adhesive Tape Industry

PU-HMA - Color Stability

Irganox

1726 provides excellent color stability in PUR hot melt adhesives (130 C)
CONTROL

80

Yellowness Index Ageing at 130 C

60

40

0.5% Irganox 245

20

0.5% Irganox 1726

0

Time (Hours)
AO were added to the HMA at 90 C Oven ageing at 130 C in alu dishes in recirculating air oven
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promoting the Interest of the Self Adhesive Tape Industry

Summary II - Hot Melts/PSA

Irganox

1726 is an effective antioxidant for SIS and SBS hot melt adhesives
outstanding mixing stability excellent color stability excellent viscosity retention efficient at low concentration

Irganox

1726 is suitable for PU-HMA

excellent color stability

Irganox

1726 is also effective in PSA application

excellent tack retention especially at high temperature
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promoting the Interest of the Self Adhesive Tape Industry

Summary II - SEBS Hot Melts

Irganox

HP 2225 is an effective antioxidant for SEBS hot melt adhesives

excellent color stability excellent viscosity retention

Irganox

HP 2225 is also suitable for EVA and APAO systems

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promoting the Interest of the Self Adhesive Tape Industry

Approvals
Irganox

1726 has the major approvals for hot melt adhesives

FDA Approvals Listed on Directive 2002/72/EC

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promoting the Interest of the Self Adhesive Tape Industry

Outlook
SIS

shortage

Irganox 1726 may help to prepare -SIS low SBS/SIS hot melt adhesive
Cable

harnessing

Irganox 1726 in conjunction with Irganox 565 may help to fulfill more stringent requirements in the automotive area for higher temperature
UV-curable

Systems

Irganox 1726 is still effective after UV curing

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promoting the Interest of the Self Adhesive Tape Industry