Synthetic Resins: Polymers

Poly (Vinyl Acetate) 1930s

Relatively stable but low Tg causes embedding of dust and dirt

Paraloid B-72 (ethyl methacrylate / methyl acrylate copolymer)

R1=C2H5; R2=CH3 / R1=CH3; R2=H)

Very stable but requires aromatic solvent

Poly(butyl methacrylate)

*
O

O C
CH3

Poly (Alkylmethacrylates) 1950s

H
C C
H2

R2
C C
H2

*
C O

R1=C4H9; R2=CH3
Soluble in mineral spirits but crosslinks upon aging

R1

Polymeric varnishes generally produce a different appearance

than natural resin varnishes.

April 2011

The Properties of Resins Used for Varnishing and Retouching of Paintings

25

Synthetic Low Molecular Weight Resins

Oligomers rather than polymers

Molecular weights typically below a few thousand
Can produce an appearance similar to that achieved with natural resins
Only those soluble in hydrocarbon solvents of interest

Ketone (Polycyclohexanone) Resins - 1950s

From cyclohexanone, methylcyclohexanones & formaldehyde

MS2 (Howards, Laporte)
AW2, Ketone Resin N, Laropal K 80 (BASF)
Not very stable and all discontinued

Chemically Reduced Ketone Resins - 1960s

O
CH2

CH2OH
CH3

OH

OH
CH2

MS2A, MS2B (Howards, Laporte; currently Linden)

More stable but brittle

April 2011

O
CH2

The Properties of Resins Used for Varnishing and Retouching of Paintings

OH
CH2
CH2OH
n

CH3

26

Synthetic Low Molecular Weight Resins

Urea-Aldehyde Resins (BASF) - 1990s

From aldehydes & urea:

Experimental Aldehyde Resin (not available)
Laropal A 81 requires 30-40% arom.
Laropal A 101 requires ca. 50% arom.
Not to be confused with Laropal K 80!
Considerably more stable than ketone resins

H3C
H3C
MeO

C
O

CH3
CH3

CH3
C C C
H2
CH3 O
CH3 OMe

C N
H2
H3C

CH3
O

C C C N
H2
H2
CH3
MeO
H3C

Hydrogenated Hydrocarbon Resins -1990s

Pure, saturated hydrocarbons: many available

Arkon P Resins (Arakawa) e.g. Arkon P 90
Regalrez Resins (Eastman) e.g. Regalrez 1094
Styrene
Soluble in aliphatic hydrocarbon solvents (0% aromatics)
Insoluble in acetone and the lower alcohols
Arkon resins not recommended; Regalrez resins most stable

April 2011

CH3

C C
H2
CH3

CH3
CH3
OMe

CH3

CH3
C CH2

H
C CH2
+
n
-Methylstyrene

Hydrogenated Hydrocarbon Resin

Regalrez Resins

The Properties of Resins Used for Varnishing and Retouching of Paintings

27

Molecular Weight Distribution (SEC)

of Low Molecular Weight Resins
Approximate Molecular Weight
100000

30000

10000

3000

1000

300

100

44

Average Molecular Weights:

Dammar
Resin

39

Intensity (V)

34

29

Regalrez 1094
Arkon P 90
24

Laropal K 80
Experimental Aldehyde Resin

Resin

Mw

Mn

Mw/Mn

Dammar

1616

528

3.06

Laropal K 80

725

459

1.58

MS2A

1561

586

2.66

Arkon P 90

872

531

1.64

Regalrez 1094

930

573

1.62

Exp. Ald. Resin

1147

644

1.78

Laropal A 81

3640

1266

2.88

Laropal A 101

2979

1179

2.53

Laropal A 101
19

MS2A
Laropal A 81

14
600

700

800

900

1000

1100

Retention Time (sec)

April 2011

The Properties of Resins Used for Varnishing and Retouching of Paintings

28

Stability of
Synthetic Low Molecular Weight Resins

Light Aging in
Xenon Arc Weather-ometer
UV component Included

UV

Visible

Xenon BS/SL
Arizona Daylight

300

350

400

450

500

550

Wavelength (nm )

600

650

700

750

Urea Aldehyde Resins

20

Solvent Removability

Lar. A 101

15

200

Lar. A 81
A 81 / 2% Tin 292
A 101 / 2% Tin 292

10
5

Stabilized with Tinuvin 292

1000

2000

3000

Aging Time (Hours)

200

Unstabilized
Dammar

Solvent Strength

Ketone Resin - 3%

Ketone) Resin
(Laropal K80)

Reduced Ketone Resin (MS2A)

MS2A - 1%

100

Aldehyde Resin - 0.5 %

100

Arkon P 90 - 1%

Dammar - 3%

Solvent Strength

Solvent Strength

25

1000

2000
3000
Aging Time (Hours)

Arkon P 90 - 2%

4000
5000
Regalrez 1094 - 0.5%

6000

Arkon P 90
Regalrez 1094

April 2011

1000

2000

Aldehyde Resin

3000
4000
Aging Time (Hours)

5000

6000

The Properties of Resins Used for Varnishing and Retouching of Paintings

30

FTIR: Hydrogenated Hydrocarbon Resins

100

100

90

90

80

80

0 HOURS

70

70

60

894 HOURS

50

50

40

40

30

30

20

20

10
0
4000

3000

2500

2000

-1

1500

1000

4779 HOURS

10

Arkon P90 Unstabilized

3500

0 HOURS

60

500

0
4000

Arkon P90 + 1 % Tin 292

3500

3000

WAVENUMBER (CM )

100

100

90

90

80

80

0 HOURS

894 HOURS

60

-1

1500

1000

500

0 HOURS

50

40

40

30

30

20

20

Arkon P90 + 1 % Tin 292

10

4679 HOURS

60

50

Regalrez 1094 + 0.5 % Tin 292

10
0

3500

3000

2500

2000

1500
-1

WAVENUMBER (CM )

April 2011

2000

70

70

4000

2500

WAVENUMBER (CM )

1000

500

4000

3500

3000

2500

2000

1500

1000

500

-1

WAVENUMBER (CM )

The Properties of Resins Used for Varnishing and Retouching of Paintings

31

SEC: Laropal A81

Unstabilized

30

2% Tinuvin 292
30

T=0

29

29

T=1500

28

28

Intensity (V)

Intensity (V)

T=1500
T=3000

T=3000

27

26

27

26

25

25

24

24

23
750

T=0

800

850

900

Time (sec)

April 2011

950

1000

1050

23
750

800

850

900

950

1000

1050

Time (sec)

The Properties of Resins Used for Varnishing and Retouching of Paintings

32

Appearance Differences
Roles of Refractive Index and Molecular Weight
Resin

Composition

nd

Regalrez 1094

Hydrogenated Hydrocarbon Resin

1.52

815

MS2A

Chem. Reduced Polycyclohexanone Resin

1.52

1773

Dammar

Triterpenoid Resin

1.54

1463

Laropal A81

Urea Aldehyde Resin

1.50

3566

Mastic

Triterpenoid Resin

1.54

6537

Paraloid B-67

Poly (Isobutylmethacrylate)

1.48

24876

Paraloid B-72

Ethylmethacrylate/ Methylacrylate Copol.

1.49

75455

AYAT

Polyvinylacetate

1.47

209596

nd = refractive index

Polymers used for varnishing have somewhat

lower RIs than low molecular weight resins.
But differences are small - much smaller than
differences in molecular weight. When
rounded off all are 1.5.
Varnish RI should be close to that of binding
medium (~1.5) to avoid reflection at the
medium-varnish interface, which generally
speaking is the case for all resins.

= weight-average molecular weight

When pigment particles are exposed at the paint surface

varnishing causes darkening because nvarnish > nair.
However greatest optical effect is due to leveling of
varnish over microscopically rough surface, which
reduces light scattering. Molecular weight differences
are very large from ~1000 to ~100,000. Low
molecular weight varnishes level more. This is the main
reason for the appearance differences.
April 2011

The Properties of Resins Used for Varnishing and Retouching of Paintings

33

Drying of Solvent-Based Varnish over

Microscopically Rough Surface
No-Flow-Point (NFP) Concept

The viscosity of the resin solution increases

during drying due to solvent evaporation.
The varnish levels until the No-Flow-Point
(NFP) is reached, after which viscosity is too
high for leveling to occur.
Subsequent shrinkage due to solvent loss causes
replication at the varnish surface of the peaks
and valleys of the paint surface, but with lower
amplitude.
The amount of shrinkage and the roughness of
the dry varnish depends on the amount of
solvent present at the NFP.
Polymer solutions have much higher viscosities
and reach their NFP with much more solvent
present than solutions of low molecular weight
resins.
Polymeric varnishes are therefore drying with
rougher surfaces

April 2011

No-Flow-Point

Dry Varnish Surface

Paint Surface
14

Height Above Lowest Valley (m)

12
10
8
6
4
2
0

The Properties of Resins Used for Varnishing and Retouching of Paintings

34

Simple Drying Model

HDF (x) = HNFP - f [HNFP HS (x)]
f=shrinkage factor (solvent fraction) - f and HNFP are constants
H NFP
H DF
HS

20% solvent at no-flow-point (f = 0.2)

April 2011

3% solvent at no-flow-point (f = 0.03)

The Properties of Resins Used for Varnishing and Retouching of Paintings

35

Quantitative Study of Varnished Surfaces:

Roughness and Light Scattering

Study in collaboration with NIST &

Universit Pierre et Marie Curie, Paris
Glass plates, ground using abrasive
compounds of different particle size
(5-19 m)
Plates look frosted white and have low
gloss
Varnishes applied from solutions in
toluene using drawdown bar
After varnishing plates look clear,
smooth and glossy
AYAT and Regalrez 1094 used as
molecular weight extremes

April 2011

The Properties of Resins Used for Varnishing and Retouching of Paintings

36