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0 20 40 60 80 100 NONVOLATILE, %

OIL PAINT

ALKYD

LACQUER

ACRYLIC X-LINKED

PE X-LINKED

HS AUTOMOTIVE

HS INDUSTRIAL

NONVOLATILE OF COATINGS

SL2319

0

1000

2000

3000

4000

5000 M

illio

n lb

s.

1996 2001 Year

Other

Chlorinated

Glycols

Glycolether & acetate

Esters

Ketones

Alcohol

Aromatic

Aliphatic

Coating SolventsUSA

SL2300

0

1000

2000

3000

4000

5000 M

illio

n lb

s.

1996 2001 Year

OEM ArchitecturalSpecial Purpose Thinner, Cleaners, Export

Coatings SolventsEnd Use

SL2301

0

200

400

600

800

1000

1200 M

illio

n Lb

s.

YEAR 1996

Machinery

Transportation

General metal

Magnet Wire

Magnetic media

Release coating

Coil coating

Automotive

Metal container

Wood furniture

Solvents Coatings OEM

SL2302

0

200

400

600

800

1000 M

illio

n Lb

s.

YEAR 1996

MISC

Interior WB

Exterior WB

Interior SB

Exterior SB

Solvents Coatings Architectural

SL2304

0

200

400

600

800

1000

1200 M

illio

n Lb

s.

YEAR 1996

Misc.

Fire Retardant

Deck and waterproofing

Marine

Traffic paint

Maintenance

Aerosol

Auto refinishing

Roof

Solvents Coatings Special Purpose

SL2305

APPLICATION OF HIGH SOLIDS

METHOD

BRUSHROLLERSPRAYDIP

VISCOSITY

RHEOLOGYSHEAR RATESAGGINGLEVELINGVITRIFICATION

1E-3

1E-2

1E-1

1E0

1E1

1E2

1E3

1E4

1E5

1E6

SHEA

R R

ATE,

(SEC

-1)

MIXDIS

PUM DIPFLO

SPRROL

BRU SAGLEV

SL2320

PREP. APPLICATION

FILM

SHEAR RATE DURING COATING OPERATIONS

DIFFERENCEREGULAR-HS-WATER

REGULAR HIGHSOLIDS

WATER

MW 1500-5000 300-1200 +1500VISCOSITY 100 P, ºC 50-120 10-50 50

OH # 50-100 120-300 0-100

COOH # <10 <10 20-100

SOLUBILITYPARAMETER p

LOW MEDIUM HIGH

PROBLEM AREAS HIGH SOLIDS

VISCOSITY SOLIDSRHEOLOGY SAGGING

ORANGE PSURFACE TENSION CRATER

CRAWLINGBERNARD

STABILITY REACTIVITYDURABILITY NETWORK

-1

-0.5

0

0.5

1

1.5

2

2.5

3

VISC

OSI

TY (l

og P

OIS

E)

5 10 15 20 25 30 SQUARE ROOT NUMBER AVERAGE CHAIN LENGT

VISCOSITY MEASURED VISCOSITY CALCULATE

VISCOSITY vs. CHAIN LENGTHDECAMETHYLENE ADIPATE POLYESTER

SL2307

1.5

2

2.5

3

3.5

VISC

OSI

TY (l

og P

OIS

E)

0 50 100 150 200 TIME IN MINUTES at 109°C

CALCULATED MEASURED DATA POINTS

VISCOSITY OF POLYESTER BLEND

SL2308

1E-1

1E0

1E1

1E2

1E3

1E4

1E5

VISC

OSI

TY, P

OIS

E

0 20 40 60 80 100 TEMPERATURE, °C

VISCOSITY as a FUNCTION OF Tg,WLF EQUATION

27 7

-13- 33- 53- 73

SL2309

log. ( ). ( )

µ = −−

+ −13

17 44516

T TgT Tg

WLF EQUATION

1E1

1E2

1E3

1E4

1E5

VISC

OSI

TY, C

PS

0 500 1000 1500 2000 2500 3000 3500 MW WEIGHT AVERAGE

POLYMER A Tg=190°K POLYMER B Tg=250°K

VISCOSITY-MOLECULAR WEIGHT 65°CLOG(VISC)= A + C*SQRT(Z)

SL2310

VISCOSITY OF POLYMER SOLUTIONS

s pTg Tg c Ws= − *

1 1

1

2

2

1 2

sTg

WTg

WTg W W K= + + ∗ ∗

1E-1

1E0

1E1

1E2

1E3

1E4

VISC

OSI

TY 2

5°C

, PO

ISE

0 0.1 0.2 0.3 0.4 WEIGHT FRACTION OF SOLVENT

ACETONE MEKMIBK CYCLOHEXANONE

VISCOSITY OF K-FLEX UD-320IN KETONES

SL2314

1E-1

1E0

1E1

1E2

1E3

1E4

VISC

OSI

TY 2

5°C

, PO

ISE

0 0.1 0.2 0.3 0.4 WEIGHT FRACTION OF SOLVENT

METHANOL ETHANOL i-PROPANOL n-BUTANOL

VISCOSITY OF K-FLEX UD-320IN ALCOHOLS

SL2315

1E-1

1E0

1E1

1E2

1E3

1E4

VISC

OSI

TY 2

5°C

, PO

ISE

0 0.1 0.2 0.3 0.4 WEIGHT FRACTION OF SOLVENT

ACETONE METHANOL BU ACETATE WATER

VISCOSITY OF K-FLEX UD-320IN SOLVENTS

SL2316

-100

-50

0

50

100

150

200

250

300

Tg in

K

0 500 1000 1500 2000 2500 MOLECULAR WEIGHT

K=25000

K=50000

K=100000

25000 50000 100000

Tg vs MOLECULAR WEIGHTOF OLIGOMERS

SL2311

Tgo = Tg -Tgo = Tg - K

Mn

Glass Transition Temperature of Polyester Resins °KDicarboxylic Diol Tg exp Tg calc exp-calcSuccinic 1,2-ethylene 272 255 17Succinic 1,4-butane 233 239 -6Succinic 1,6-hexane 220 230 -10Succinic 1,7-heptane 228 226 2Adipic 1,10-dodecane 217 215 2Sebacic 1,4-butane 216 219 -3Sebacic 1,4-butene 233 225 8Sebacic 1,4-butyne 246 231 15Terephthalic 1,2-ethylene 345 346 -1Terephthalic 1,4-butane 307 302 5Terephthalic 1,6-hexane 264 277 -13Terephthalic 1,10-dodecane 268 251 17Terephthalic bisphenol A 478 465 13Isophthalic 1,2-ethylene 324 346 -22

1E0

1E1

1E2

1E3

1E4

VISC

OSI

TY, p

oise

0 0.1 0.2 0.3 0.4 PIGMENT VOLUME CONCENTRATION OF PAINT

PAINT PAINT FLOCC.PAINT ADSORB. PAINT ADSORB. FLOCC

MOONEY EQUATIONTiO2 PIGMENTED COATING

SL2318

0 10 20 30 40 50 dyn/cm

PE 2 FUNCTPE 3 FUNCPE 4 FUNC

PE HSACRYL COOH

BuMAEMA

HMMMTBTMMHBMM

POLY

MER

SURFACE TENSION

SL2092

CRAWLINGCRAWLING

CRATERSCRATERS

WETTINGWETTING

BERNARD CELLBERNARD CELL

-1

0

1

2

3

4

VISC

OSI

TY L

OG

PO

ISE

0 2 4 6 8 10 BAKING TIME, MINUTES

PTSA NO SCA PTSA SCA PTSA BL1 SCA PTSA BL2 SCA

SL2319

SAGG CONTROL AGENT

SAG TESTSAG TEST

SL2100

!! ATTAPULGITEATTAPULGITE!! SMECTITESMECTITE!! ASSOCIATIVEASSOCIATIVE!! SILICASILICA!! TITANATETITANATE!! POLYESTERPOLYESTER!! POLYACRYLATEPOLYACRYLATE

!! POLYOLEFINPOLYOLEFIN!! ORGANO CLAYORGANO CLAY!! ORGANO SULFONATE ORGANO SULFONATE !! POLYAMIDE POLYAMIDE !! CASTOR DERIVATIVECASTOR DERIVATIVE!! POLYUREAPOLYUREA!! CATIONIC OLIGOMERCATIONIC OLIGOMER

RHEOLOGY MODIFIERRHEOLOGY MODIFIER

FACTORS INFLUENCING VISCOSITYPOLYMER

GLASS TRANSITION TEMPERATURE , TgFUNCTIONAL GROUP CONTENT

TEMPERATURE

SOLVENTSOLVENT POLYMER INTERACTION

SOL VENT VISCOSITYSOLVENT CONTENT

CROSSLINKER

MOLECULAR WEIGHT & DISTRIBUTION

ADDITION VERSUS CONDENSATION

PIGMENTPARTILE SIZE AND SHAPE

LOADING AND DISPERSION

NR-NCO

O

N

N OO

R-NCO

OCN-R

O||

OCN-R-NH-C-N-R-NCO|

O=C-R-NCO

O||

OCN-R-N-C-O-R-NCO|

O=C-R-NCO

N-R-NCOOCN-R-N

O||

||O

ISOCYANATE CROSSLINKER

N

N

N

N

N NCH2-O-CH3

CH2-O-CH3

CH2-O-CH3

CH3-O-CH2

CH3-O-CH2

CH3-O-CH2

HMMM

1

2

3

4 VI

SCO

SITY

(log

PO

ISE)

0 50 100 150 200 TIME IN MINUTES at 109°C

CALCULATED MEASURED DATA POINTS

VISCOSITY OF POLYESTER BLEND

SL2308

-1

-0.5

0

0.5

1

1.5

2

2.5

3

VISC

OSI

TY (l

og P

OIS

E)

5 10 15 20 25 30 SQUARE ROOT NUMBER AVERAGE CHAIN LENGT

VISCOSITY MEASURED VISCOSITY CALCULATE

VISCOSITY vs. CHAIN LENGTHDECAMETHYLENE ADIPATE POLYESTER

SL2307

1E-1

1E0

1E1

1E2

1E3

1E4

VISC

OSI

TY, P

OIS

E

0 20 40 60 80 100 TEMPERATURE, °C

VISCOSITY as a FUNCTION OF Tg,WLF EQUATION

27 7

-13- 33- 53

- 73

SL2309

1E1

1E2

1E3

1E4

1E5

VISC

OSI

TY, C

PS

0 500 1000 1500 2000 2500 3000 3500 MW WEIGHT AVERAGE

POLYMER A Tg=190°K POLYMER B Tg=250°K

VISCOSITY-MOLECULAR WEIGHT 65°CLOG(VISC)= A + C*SQRT(Z)

SL2310

-100

-50

0

50

100

150

200

250

300

Tg in

K

0 500 1000 1500 2000 2500 MOLECULAR WEIGHT

K=25000

K=50000

K=100000

Tg vs MOLECULAR WEIGHTOF OLIGOMERS

Tgo = Tg - K

Mn

K IS A CONSTANTS .

SL2311

0

50

100

150

200

250

300

VISC

OSI

TY (P

OIS

E)

0 1 2 3 4 5 HYDROXYL mol/1000

VISCOSITY vs. HYDROXYL CONTENTNPA/NPG/TMP/DIBASIC ACID

SL2317