Hydrophobing additive for impregnation

and primers

Impregnation is performed on building Primers are used to reduce the absor-

materials when it is not intended to coat bency and consolidate the substrate. For
them further. The aim of impregnation is this, the primer must be able to penetrate
to reduce the water uptake of a building the substrate adequately. Otherwise, too
material without otherwise altering its much material would remain on the sur-
characteristics such as porosity or appear- face and consolidation of the substrate
ance. The impregnating agent must not would not be sufficient. Adhesion prob-
impair water vapor and carbon dioxide lems might arise with subsequent coats.
permeability. Impregnation with siloxane The right primer can have a decisive influ-
products can be achieved with TEGO® ence on the durability of the complete
Phobe 6010 for solvent-based impregna- coating system.
tion or TEGO® Phobe 6510 and 6600 for
water-based impregnation. Impregnation Effective priming protects the coating
should not be used for materials which from infiltration of salts and water which
have little or no absorbency. can damage the building. If the top coat is
damaged, the primer must additionally
protect the building material from further
damage by water penetration.

With siloxanes of the TEGO® Phobe 6xxx

Figure 5: Measuring of water absorption series, Evonik offers products for formu-
lating solvent- and water-borne primers.

Test blocks Water Test methods

PU-foam Bath
Determination of water vapor permea-
bility by the wet cup method

Evonik uses a gravimetric method from

EN ISO 7783-2 to determine the water
vapor permeability by comparison with an
inert carrier material. The substrates are
polyethylene frits with a diameter of 60
mm. The coating material is applied to the
frit with a flat brush in the amount per

page 118 Technical Background_Hydrophobing Agents

unit area recommended for use in prac-
tice. If details of the amount to be applied
for a given area are not available, Evonik
applies the paint in two coats using 400
ml/m² in total. The coating is dried
­overnight in a standard climate (23°C, Wet-Cup Dry-Cup
50% relative humidity) followed by 24
hours at 50°C.

A weighing dish with a diameter of 61 Coating

mm and height of 30 mm is filled with 20 Glass frit
100% relative 0% relative
ml of distilled water. A small sponge is humidity humidity
placed in the dish to stop the underside of
the frit coming into contact with liquid water Balance
glass
P2O5
which could otherwise invalidate the Climatic chamber: 23°C / 50% relative humidity
measurement. The dish is closed with the
Figure 6: Wet-cup method
coated frit and the joint between the frit
and the weighing glass sealed with hot
melt adhesive. The whole is then weighed
accurately using an analytical balance to
±0.1 mg and kept for five days in a cli-
mate chamber at 23°C and 50% relative
humidity. After this, it is weighed again. and the glass is then kept in a standard cli- The correct amount of coating is then
By comparison with a non-coated speci- mate of 23°C and 50% relative humidity. poured onto the block and distributed
men, the amount of water diffused is The water vapor diffusion is thus in the with a flat brush ensuring that the sides
determined from the weight loss of the opposite direction. are coated as well. The amount of coating
sample (fig. 6). The performance of the material is based on the recommended
test can be seen on our internet site under Comparison of wet- and dry-cup methods amount used in practice. If there are no
“Measurement of water vapor permeabil- has shown that the wet-cup method is recommendations as to the amount to be
ity (sd-value)”. more accurate. used for a given area, Evonik uses a total
of 400 ml/m² applied in two coats. Care
must be taken to ensure that all the pores
Determination of water vapor permea- Measurement of capillary water uptake of the block are closed. The coated block
bility by the dry cup method is kept overnight in a standard climate
The capillary water uptake is measured (23°C, 50% relative humidity) followed
The dry-cup method is another way of by Evonik from EN 1062-3. The test by drying for 24 hours at 50°C.
measuring the water vapor permeability. specimens are calcium sandstone blocks
Preparation of the sample is the same as with an area of 115 x 70 mm = 0.008 m2
that for the wet-cup method. However, in and a thickness of 20 mm. The blocks are
the dry cup method the weighing dish is prepared by scrubbing them free of dirt
filled with phosphorous pentoxide (P2O5) with water and then drying for 24 hours
to produce an internal humidity of 0% at 50°C.

Technical Background_Hydrophobing Agents page 119

 The test samples are placed on foam in a Determination of the contact angle
water-filled tray (fig. 5). The level of the
water must reach the underside of the The contact angle describes the wettabil-
samples and from time to time the water ity of a substrate by a liquid, predomi-
level is checked and water replenished if nantly water in the case of exterior paints.
necessary. After 24 hours, the blocks are To determine the contact angle, a water
removed from the water bath, placed on droplet with a specified volume is placed
paper, blotted and weighed. DIN EN on the coating. Using an optical method,
1062-3 specifies a fourfold watering of the angle of the tangent of the drop to the
the block. In the first watering, water-sol- substrate is measured. High contact
uble components of the coating are angles indicate poor wetting and conse-
washed out. For classification of EN ISO quently good water beading. In contrast,
1063-1, the result of the fourth watering low contact angles indicate good wetting
is taken and specified as the w24-value, and poor water beading. The contact
e.g. w24 = 0.5 kg/(m2 · √h) angle can change during the course of the
measurement. In particular, with fresh
The method of measuring the capillary paints which have not been exposed to
water uptake can also be seen on our water or weathering, the contact angle
internet site. decreases during the course of the mea-

page 120 Technical Background_Hydrophobing Agents

surement. The reason for this is that Dirt pick-up tains both organic and inorganic matter
emulsifiers and other water-soluble com- such as would typically be found in highly
ponents are dissolved out of the paint film In addition to the technical properties of a polluted urban or industrial areas. The
and these lower the interfacial tension of coating, it is also important that it retains results of the soiling test are specified as
the water droplet. If the coating is irri- its appearance over a long period of use. delta L of the sample before and after the
gated for 24 hours prior to the measure- One obvious visible aspect of an exterior test. Experience shows that this soiling
ment, higher and more stable values of coating is its soiling characteristics. This test produces results which would other-
the contact angle are obtained. When can be tested in several years of outdoor wise only be obtained by several years of
comparing results of contact angle mea- weathering but the tendency of an exter- outdoor weathering tests.
surements, it is therefore always neces- nal coating to soil can be simulated in a
sary to know details of the pre-treatment. fast test developed by Evonik. Using a
converted washing machine, test samples
No statements about the capillary water of coatings are sprayed with a dirt disper-
uptake can be made from the contact sion and then dried. This is repeated sev-
angle of a coating. eral times. The dirt dispersion used con-

Determination of the contact angle using an optical method.

Technical Background_Hydrophobing Agents page 121

 FAQs

Vertical tracks which differ from the We have found that our silicone resin
original color are caused by rain. How paints show a strong increase in viscosity
can this sensitivity to sudden rain of a after storing for 5 to 6 months. How can
recently applied silicone resin paint be we prevent this?
improved? The order of addition during the manu-
We offer TEGO® Phobe 1650, a silicone facture of the paint plays an important
resin with early water resistance. That role. After manufacturing the millbase,
means that the hydrophobic effect of the silicone resin emulsion should be
TEGO® Phobe 1650 develops very added first and the binder dispersion
quickly after application. According to the only added after further stirring.
method for determination of capillary
water uptake, EN 1062-1, coatings must How much silicone resin do I need to
reach their full effectiveness after the formulate a silicone resin paint?
fourth exposure to water. TEGO® Phobe There is no clear rule as to how much sili-
1650 actually achieves this after only two cone resin a formulation must contain.
exposures. More important than the quantity used is
that the formulation must fulfill the physi-
Does the silicone resin in silicone facade cal demands made on it, such that it
paints affect the sd value and is the PVC achieves class 3 in permeability of water
of the coating altered? and class 1 in water vapor transmission
The amount of silicone resin has practi- rate. Older formulations contain up to
cally no effect on the sd-value. Investiga- 10% silicone resin emulsion to satisfy
tions have shown that silicone resins do these demands. With the newest genera-
not behave like binders in their effect on tion of silicone resin emulsions, similar
wet abrasion resistance or sd-value. In cal- properties can be reached with only
culating the PVC, silicone resins should 4 to7%.
therefore not be incorporated into the
calculation as binders.

page 122 Technical Background_Hydrophobing Agents

In choosing the silicone resin, it should be (The abbreviations M-, D-, T- and Can I improve the wet abrasion resis-
noted that, by definition, silicone resin Q-units are explained in the section tance of a coating by using silicone
paints must be made hydrophobic with a “Chemistry of silicone products” in this hydrophobing additives?
silicone resin. Even if linear polysiloxanes chapter.) Investigations have shown that silicone
can produce a similar hydrophobing effect hydrophobing materials have only a slight
they cannot, by definition, be used to How is a silicone resin defined? effect on wet abrasion resistance.
hydrophobe silicone resin coatings. Silicone resins are silicone structures that
contain branching T- and/or Q-units. Can I impart especially good cleaning
How do silicone resin paints behave with They can also contain linear components properties to a matte interior paint by
respect to dirt pick-up? of D- and M-units. Depending on the adding silicone resins?
The claim that silicone-containing coat- amount of linear components, customized Producing a hydrophobic paint surface by
ings with a high water-beading effect are resins with high or low hardness can be adding silicone resin is not sufficient to
self-cleaning has not been shown in prac- formulated. impart good cleaning properties to a coat-
tice. On the contrary, silicones in coatings ing. Whether or not a coating can be
tend to promote soiling of the surface. As Should silicone resin hydrophobing addi- cleaned easily is determined by the overall
silicones are necessary to reduce the cap- tives be regarded as binders? formulation. A silicone hydrophobing
illary water uptake, it is necessary to find Silicone resin paints are formulated with additive can nevertheless contribute to
the best compromise amount. With the an organic binder dispersion and a sili- the cleanability of the coating.
most recent generation of silicone resins, cone resin. Often the amount of binder
between 4-7% produces a good balance dispersion is in the region of 8 to 20% Can I make deductions about the capil-
between dirt pick-up and capillary water and that of the silicone resin between 4 lary water uptake of a paint from the
uptake. and 10%. If the amount of silicone resin contact angle?
in the formulation is altered and coating The contact angle and the capillary water
What is the difference between a sili- properties such as water vapor transmis- uptake refer to two fundamentally differ-
cone resin and a silicone oil? sion or wet abrasion resistance compared ent things. The contact angle describes
In terms of chemical structure, silicone with a formulation in which the organic the wettability of a coating surface by
resins and silicone oils differ in the way binder has been altered by a similar water. High contact angles indicate poor
the molecules are branched. Silicone oils amount, it is noticeable that both formu- wettability and a concomitant water
(also known as polysiloxanes) have a lations do not change in the same way. beading effect. The capillary water uptake
­linear structure composed of M- and Raising the amount of organic binder describes the capillary hydrophobicity of a
D-units. Silicone resins are branched and leads to a higher water vapor diffusion coating. It is quite possible for a coating to
contain T- and/or Q-units. Silicone resins resistance and a higher wet abrasion have high (and consequently unfavorable)
which contain only T- and Q- units have resistance; whereas these two properties capillary water uptake even though the
a very closely meshed resin network and remain virtually unchanged for changes in beading effect is very strong.
high hardness. If they also contain D- silicone resin. This indicates that the sili-
and/or M-units, the resin forms a more cone resin is not behaving as a binder. It is
open network with lower hardness. The therefore questionable if the silicone resin
real physical difference between a silicone should to be included as a binder when
oil and a silicone resin is the film forming calculating the PVC.
properties. Silicone oils do not form films;
that is to say that from an emulsion or
solution they dry to an oily layer. In con-
trast, silicone resins form a non-tacky soft
to hard silicone resin film.

Technical Background_Hydrophobing Agents page 123

Co-Binders
TEGO® AddBond – TEGO® VariPlus
 TEGO® AddBond
Polyester resins as co-binders
Adhesion is a key topic in coatings sys- range of polyester resins which improve
tems. The demands made on adhesion- adhesion of solventborne, waterborne
promoting products are highly sophisti- and radiation-curing coatings and printing
cated. Besides excellent compatibility inks regardless of the way they dry or
with other formulation components, such cure. The resins can be used in physically
resins must be able to optimize adhesion drying, oxidatively drying, heat-curing
on all types of substrates. TEGO® Add- and radiation-curing systems.
Bond products provide formulators with a

O O O O O O
– (2n – 1) H2O
n HO R1 OH + n HO R2 OH HO R1 O R2 O H HO R1 O R2 O H
n COO  NR
-
4
+ n
Figure 1: General reaction (schematic) for the manufacture of TEGO® AddBond resins Figure 2: Structure of an aqueous dispersion of a
TEGO® AddBond resin

How are polyester resins manufactu- boxyl groups with amines (fig. 2). Such
red? solvent-free dispersions have a good stor-
age life. The TEGO® AddBond resins are
TEGO® AddBond resins are polyester resistant to hydrolysis. They always con-
­resins with a special structure. They are tain free carboxyl and hydroxyl groups.
manufactured by the polycondensation of Their hydrophilic and hydrophobic char-
special-purpose carboxylic acids and poly- acteristics are designed to make a maxi-
ols (fig. 1). Aqueous secondary disper- mum contribution to improving adhesion
sions are obtained by neutralizing car- and enhancing corrosion protection.

Technical Background_Co-Binders page 125

 Some properties of TEGO® AddBond products

Viscosity Softening Acid value Hydroxyl value

Product Supply form (23°C, mPa · s) temperature (°C) (mg KOH/g) (mg KOH/g)

TEGO® AddBond LTH solid 600 – 15001 90 – 102 12 – 20 ~ 252

TEGO® AddBond LTW 60 % in xylene 350 – 650 soft resin 20 – 30 ~ 302

TEGO® AddBond LTW-B 60 % in n-butyl acetate 350 – 650 soft resin 20 – 30 ~ 302

TEGO® AddBond 2220 ND 60 % in Solvesso 150 1500 – 2700 soft resin 18 – 22 ~ 302

TEGO® AddBond 2325 60 % in n-butyl acetate 300 – 700 ~ 60 ~ 18 ~ 162

TEGO® VariPlus 3350 UV 50 % in TPGDA ~ 8000 ~ 60 ~ 18 ~ 162

TEGO® AddBond 1270 70 % in sec-butanol 4000 – 9000 soft resin 56 – 65 ~ 252

TEGO® AddBond DS 1300 45 % in water ~ 150 ~ 55 – ~ 602

TEGO® AddBond HS 75 % in n-butyl acetate 1500 - 2500 soft resin 20 - 30 ~ 1002

1
60% in xylene 2
solid resin Table 1

What do polyester resins achieve? sion which does not contain any organic for use in multicoat finishes. In effect-
solvents. All other products are dissolved finishes, they improve cohesion within
With the exception of TEGO® AddBond in an organic solvent. the film. The adhesion promoting proper-
LTH, which is a solid resin, all other prod- ties of TEGO® AddBond products, com-
ucts in the TEGO® AddBond range are TEGO® AddBond resins contribute to plemented by excellent resistance to
supplied as solutions (table 1). Since improved adhesion on numerous sub- hydrolysis, significantly improve the anti-
TEGO® VariPlus 3350 UV is also a poly- strates. They are effective on metals, min- corrosion performance of coatings.
ester resin, it is listed here. This resin is erals and various plastics and are thus TEGO® AddBond resins help to enhance
dissolved in tripropyleneglycol diacrylate, often used in primers or one-coat fin- gloss, flexibility and hardness.
a UV-reactive solvent. TEGO® AddBond ishes. They also improve intercoat adhe-
DS 1300 is an aqueous secondary disper- sion so they are highly recommended

Figure 3: Use of
TEGO® AddBond LTW
in coil coatings

page 126 Technical Background_Co-Binders

 Areas of application of TEGO® AddBond resins

LTW/ VariPlus
HS LTH LTW-B 2220 ND 2325 1270 DS 1300 3350 UV

Can Coating + – + + o – – –

Coil Coating + – + + o – – –

Automotive OEM finishes + o + – – – + –

Container lacquers + o + o + o – –

Floor coatings – + – – – – – –

Metal finishes + + + + + + + –

Can coating lacquers + + + + – o + –

Finishes for plastics + + + + + + + + (UV)

Anti-corrosion paints + + + – + + + –

Primers (air-drying) – + – – o – + –

Primers (baking systems) + o + + o o + –

Printing inks – + – – – – – + (UV)

Road marking paints + + + + + – – –

Waterborne coatings – – – – – + + –

Adhesives + + + – o o + o (UV)

Hot embossing foils – + – – – – + –

UV coatings – + – – – – – +

+ recommended use o possible use – limited use

TEGO® AddBond resins are used as co- An additional important area of applica-
binders in numerous paints and lacquers tion is automotive OEM or refinish coat-
such as can coatings and coil coatings, ings. TEGO® AddBond LTW and LTW-B
automotive OEM or refinish coatings, are widely used in solventborne finishes.
industrial coatings, anti-corrosion paints, TEGO® AddBond 1270 is used in brake
road marking paints, printing inks, adhe- disc lacquers. TEGO® AddBond DS 1300
sives, hot embossing foils and UV coat- is used, for example, to improve the adhe-
ings. sion of waterborne paints on plastic fend-
ers (fig. 4).
Figs. 3 to 7 show typical examples of
applications. TEGO® AddBond LTW and TEGO® AddBond products are also used
LTW-B improve adhesion of can coatings in anti-corrosion paints, TEGO® AddBond
and coil coatings (fig. 3). These resins LTH and LTW in solventborne coatings,
exhibit a flexibilizing effect and enhance and TEGO® AddBond DS 1300 in water-
the coating’s processing properties. borne coatings (fig. 5).

Technical Background_Co-Binders page 127

Figure 4: Use of TEGO® AddBond DS 1300 in automotive Figure 5: Use of TEGO® AddBond LTH in anti-corrosion paints
finishes

TEGO® AddBond products improve adhe- 1300 and 1270 for waterborne finishes acrylic resins and reactive thinners,
sion in numerous paints and lacquers for and TEGO® AddBond LTH and TEGO® TEGO® VariPlus 3350 UV is recom-
plastics substrates such as polyamide, VariPlus 3350 UV for radiation-curing mended for use in radiation-curing coat-
polyvinylchloride, polycarbonate, ABS, coatings. The flexible TEGO® AddBond ings, printing inks and adhesives (fig. 7).
ABS/polycarbonate, Noryl or HIPS. The LTW ensures good substrate wetting, TEGO® AddBond LTH is also used in
TEGO® AddBond products LTH, LTW, improved adhesion and excellent cohesion some UV formulations. Both resins
LTW-B, 2325 and 1270 are recom- of effect pigment finishes (fig. 6). enhance not only adhesion but also
mended for solventborne finishes, DS Because of its high compatibility with reduce volume shrinkage during curing.

Figure 6: Use of TEGO® AddBond LTW in plastic coatings Figure 7: Use of TEGO® VariPlus 3350 UV in UV printing inks

page 128 Technical Background_Co-Binders

 TEGO® VariPlus
Ketone-aldehyde resins and special resins derived from them

Numerous coatings and printing inks are good solubility in the solvents commonly stantially on the ketone used. If acetophe-
available commercially. Physically-drying used in these systems make them highly none or trimethylcyclohexanone are used,
coatings, air-drying paints, stoving enam- versatile. resins with exclusively keto groups are
els and radiation-curing systems are used obtained (fig. 1). It is possible to manu-
in diverse fields and applied to very dif- facture ketone resins containing hydroxyl
ferent substrates. TEGO® VariPlus resins How are ketone-aldehyde resins and groups by using suitable reaction condi-
are frequently used to enhance the prop- the special resins derived from them tions and cyclohexanone.
erty profile of such systems. These non- manufactured?
saponifiable, neutral, hard resins have a
low molecular weight, low inherent color Ketone-aldehyde resins are manufactured
and exhibit good light and heat resistance. by an aldol condensation of a ketone with
Their outstanding compatibility with the an aldehyde. The resulting chemical struc-
most important main binders and their tures and their properties depend sub-

O O

n
HO
O
n n
Figure 1: Typical structures of
TEGO® VariPlus resins based on TEGO® VariPlus AP TEGO® VariPlus TC TEGO® VariPlus CA
ketone-aldehyde chemistry

Technical Background_Co-Binders page 129

 O
n n n
R
OH O N N O

H H
Figure 2: Typical structures of
TEGO® VariPlus SK TEGO® VariPlus 1201 TF TEGO® VariPlus resins based on
modified ketone-aldehyde resins

Another possibility for obtaining alcohol Another method ensures water-compati- hyde resins are also substantially improved.
groups is by hydrogenating the keto bility by incorporating polyether chains. The solubility of TEGO® VariPlus resins in
group. In this way, the ketone-aldehyde This enables TEGO® VariPlus UC to be organic solvents is very good. The polar-
resin TEGO® VariPlus AP is made into the used to manufacture a water-soluble poly- ity determines the solubility in very polar
polyol resin TEGO® VariPlus SK (fig. 2). etherketone resin which is also soluble in (alcohols) or very non-polar (aromatic-
The polyurethane-polyol resin TEGO® organic solvents. free white spirit) solvents. With one
VariPlus 1201 TF is manufactured by exception, all TEGO® VariPlus resins are
reacting the hydroxyl groups of TEGO® hard solids. The glass transition tempera-
VariPlus SK with a special light-resistant How do ketone-aldehyde resins and ture ranges from -47°C to +130°C.
polyisocyanate using an organotin-free special resins derived from them per- While most resins are supplied as solids,
catalyst. form? TEGO® VariPlus 1201 TF is supplied in an
organic solvent. As an aqueous secondary
Resins for waterborne applications can be As a result of their chemical structure and dispersion with excellent stability, TEGO®
manufactured by various means. Water- the production process, the ketone-alde- VariPlus DS 50 is free from organic sol-
insoluble resins, for example, are ren- hyde resins are very light in color and vents. TEGO® VariPlus UC is the only
dered water-dispersible by neutralization transparent compared with natural resins. ­solvent-free, liquid resin with a low glass
of the carboxyl groups. These polyure- The inherent color and resistance to light transition temperature of -47°C.
thane-polyol dispersions are resistant to and heat of the special resins obtained by
hydrolysis (fig. 3). chemical modification of the ketone-alde-

n n
PIC PIC
O O O O
- +
COO  NR 4

Figure 3: Structure of
TEGO® VariPlus DS 50 the water-dispersible
TEGO® VariPlus DS 50

page 130 Technical Background_Co-Binders

 Physical properties of TEGO® VariPlus resins

Color value Softening temp./ Tg OH-value

Product Supply form Gardner Melting temp. (°C) (°C) (mg KOH/g)

TEGO® VariPlus AP solid ≤3 ~ 75 ~ 50 ~5

TEGO® VariPlus TC solid ≤3 ~ 65 ~ 40 ~ 10

TEGO® VariPlus CA solid ≤2 ~ 102 ~ 75 ~ 200

TEGO® VariPlus SK solid ≤1 ~ 115 ~ 90 ~ 325

TEGO® VariPlus 1201 TF 49% in EA ≤2 ~ 163 1

~ 130 1
~ 2001

TEGO® VariPlus DS 50 33% in water – ~ 1501 ~ 120 ~ 190

TEGO® VariPlus UC liquid <7 – ~ – 47 ~ 40

TEGO® VariPlus UC W 40 40% in water – – ~ – 47 ~ 40

solid resin
1 

As a result of the optimized process, the • faster drying and set times • better mechanical resistance
formaldehyde content of products based • lower VOC content • better corrosion protection
on acetophenone is below the limits of • higher hardness • better block resistance
detectability. • higher gloss • higher pigment loading and higher
• improved adhesion color intensities through improved pig-
Because of their low molecular weights • improves ability to be used in primers ment wetting
and high softening or melting tempera- • better heat resistance • lower pigment paste viscosities
tures, resins in the TEGO® VariPlus range • better chemical resistance
are not film-forming. They are thus com-
bined with other binders to improve the
properties of coatings.

TEGO® VariPlus resins influence in all

sorts of ways the properties of solvent-
borne, waterborne and radiation-curing
coatings, printing and other inks as well
as of adhesives:

Figure 4: Use of
TEGO® VariPlus 1201 TF
in printing inks

Technical Background_Co-Binders page 131

 Areas of application of TEGO® VariPlus resins
+ recommended use
UC/UC o possible use
AP SK 1201 TF CA TC DS 50 W 40 – limited use

Wood finishes + + – + o + –

Coatings for plastics o + + + + + –

Anti-corrosion coatings + + – + o o –

Concrete coatings + – – + o – –

Road marking paints + + – + o – –

Industrial finishes + + – + o + o

Paper coatings – + + + – + –

Writing inks – + – o – + –

Adhesives + o – + + o –

Pigment pastes o o + o + + +

Printing inks – + + + – + –

Hot embossing foils – + + + – – –

UV coatings + + – o o o o

Besides their widespread use in printing marking paints, industrial finishes, pack- gloss, and good block resistance during
inks (rotogravure, flexographic, screen aging coatings, paper coatings, writing rapid drying. Because of its very good
printing, uv and specialist printing pro- inks, pigment pastes, liquid adhesives and pigment wetting, it is also used in pig-
cesses) and hot embossing foils, TEGO® hot melt adhesives. ment pastes to achieve high color inten-
VariPlus resins are proven co-binders in sity and good transparency.
coatings and adhesives. They are used in Figures 4 to 7 show typical applications.
wood finishes, coatings for plastics, anti- TEGO® VariPlus 1201 TF imparts printing
corrosion paints, concrete paints, road inks with very good adhesion, excellent

Ballpoint pen pastes owe their special

rheological properties to the unique
structure of TEGO® VariPlus SK. This
resin prevents drying out and leakage of
the ink while ensuring rapid setting after
writing.

Figure 5: Use of TEGO® VariPlus SK in ballpoint pen pastes

page 132 Technical Background_Co-Binders

Figure 6: Use of TEGO® VariPlus DS 50 in coatings for plastics

Used as a resin in the top coat of hot plastics to water, solvents and chemicals oped specifically for solventborne,
embossing foils, TEGO® VariPlus CA has as well as their film hardness and gloss. extremely high-solids pigment concen-
a positive influence on a range of proper- Substrate adhesion is also optimized. trates with high pigment loadings. TEGO®
ties such as gloss, flexibility and fastness. VariPlus UC W 40 makes this resin acces-
It is also used in the adhesive film of these TEGO® VariPlus TC has proved itself as a sible for use in waterborne (including uni-
coated foils because it enhances adhesion. grind paste resin in pigment concentrates versal) pigment preparations.
because of its universal solubility in
Because of its high glass transition tem- organic solvents, compatibility with bind-
perature and special chemical structure, ers and excellent pigment wetting.
TEGO® VariPlus DS 50 improves the TEGO® VariPlus UC represents a new
resistance of waterborne coatings for generation of pigment paste resins devel-

Figure 7: Use of TEGO®

VariPlus TC in pigment
pastes for coatings

Technical Background_Co-Binders page 133

Silicone Resins
SILIKOPHEN® – SILIKOFTAL® – SILIKOPON®
 Silicone resins and silicone combination resins

An important reason for the wide applica- These properties make silicone resins and
tion and commercial success of silicone silicone combination resins widely appli-
resins are properties such as: cable in areas such as impregnation of
• thermal stability concrete, high-temperature resistant coat-
• weathering resistance ings or weather resistant exterior coat-
• maintaining elasticity at low tempera- ings. These binders are used in the form
tures of solutions, liquid resins and emulsions.
• low surface tension
• hydrophobicity, surface activity
• release and lubricating properties

General introduction and manufacture (Si-O-Si), also found in silicates, is

ca. 280°C of silicone resins responsible for the “inorganic” character.
catalyst
Si+R-CI RxSiCI4-x The organic properties arise from the
Silicones are organic silicon compounds direct link between silicon and carbon.
Figure 1: Müller-Rochow synthesis
known as polyorganosiloxanes. This prod-
uct group can be defined simply as fol- The starting point for manufacturing sili-
lows: cone resins are the chlorosilanes which
• they are polymers are obtained on a large scale by the Mül-
• silicon is directly bonded to carbon ler-Rochow synthesis. In this, very pure
• there is at least one oxygen atom con- silicon (>98%) is reacted at 280°C in the
nected to the silicon presence of catalysts and promoters with
chemicals such as methyl chloride or phe-
The silicones occupy a hybrid position nyl chloride in a fluidized bed reactor
between inorganic and organic com- (fig. 1).
pounds, specifically between silicates and
organic polymers. The siloxane link

Technical Background_Silicone Resins page 135

 Structural units for forming polymeric siloxanes (R: methyl or phenyl groups)

Basis monomer Functionality in terms of hydrolyzable groups Structural unit in the polymer Symbol

SiX4 tetrafunctional (form spatial structures) SiO4/2 Q

R-SiX3 trifunctional (form spatial structures) RSiO3/2 T

R2-SiX2 difunctional (form chains) R2SiO2/2 D

R3-SiX monofunctional (chain breaking or terminating) R3SiO1/2 M

Table 1

The composition and number of the struc- ­ etwork of three-dimensional and cyclic
n Varying the resin intermediates and poly-
tural units and the functional groups on structures is formed. Because of this com- ols enables the following series of prod-
the silicon atom determine the structure, plexity, precise chemical structural formu- ucts to be manufactured:
processing, and complex properties of the las cannot be given. In general, silicones • "pure" phenyl methyl silicone resins
silicone resins. Table 1 shows the struc- are described in terms of their different (SILIKOPHEN®) with silicone content
tural elements for forming polyorganosi- substituents and reactive groups (fig. 3). of approximately 95%, both solvent-
loxanes. based and as aqueous emulsions
Various techniques have been developed • silicone polyester (SILIKOFTAL®) with
for further modification of the resin inter- silicone content of 30 to 80%
Silicone resin manufacture by Evonik mediates. All Evonik silicone resins are • silicone-epoxide hybrid binders
manufactured using a common reaction (SILIKOPON®) with silicone content of
Chlorosilanes, the starting materials for scheme. First, resin intermediates with 50%
silicone resins, are generally reacted with well-defined molecular weight and con- • silicone-modified, aqueous polyure-
water or alcohols (methanol or ethanol) taining almost exclusively SiOR- rather thane dispersions (SILIKOPUR®)
to produce resin intermediates with than SiOH-reactive groups are produced.
molecular weights (MW) between 1,000 These are crosslinked further with polyols Because they also con¬tain only a small
and 3,000 g/mol. These have many OH- to produce single phase products with a amount of an organic com¬ponent,
and/or OR- end-groups and no longer long shelf life. SILIKOPHEN® resins exhibit excellent
contain chlorine. During hydrolysis/alco- heat resistance. Figure 4 describes
holysis of the silane mixture, a dense SILIKOPHEN® and SILIKOFTAL® resin
manufacture at Evonik.

Crosslinking of SILIKOPHEN® and SILIKOFTAL®

silicone resins

Chemical Reactions Equations (1) and (2) describe the reac- manufacture and also during curing.
tion of chlorosilanes with water and alco- Reactions (4) to (6) are particularly
In general, only a few chemical reactions hol. They occur only during the manufac- important during manufacture as they
are important in the manufacture and cur- ture of the resin intermediate. Reactions lead to an increase in molecular weight.
ing of silicone resins (fig. 2). (3) to (6) take place both during resin

page 136 Technical Background_Silicone Resins

 (1) SiCl + H2O > SiOH + HCL 
(2) SiCl + ROH > SiOR + HCL   
(3) SiOR + H2O > SiOH + ROH  
(4) SiOH + SiOH > SiOSi + H2O   
   
(5) SiOH + SiOR > Si-O-Si + ROH      
(6) SiOR + R’OH > SiOR’ + ROH    

     
R’ = polyol residue R = CH3, C2H5      
Figure 2: Chemical reactions        
   
  


    

 

  
 
 
 
The silicone intermediates and organic 
 
components such as polyols are not com-
Figure 3: Structure of a silicone resin (idealized, R: methyl or phenyl groups)
patible with each other at the beginning
of the modification process. They only
become compatible and homogenizable
as a result of the chemical reactions. The
reaction is stopped when the desired
molecular weight is reached. Product group SILIKOPHEN®
Polyol
Phenyl-
The partially completed modifying reac- methyl silicone
resin
tion (6) is resumed during curing. This
involves further reaction of the remaining
Methyl/Phenyl
functional groups in a system which is
Silane Resin Intermediate Resins
already strongly crosslinked and for
SILIKOPHEN® and SILIKOFTAL® can only
occur at high temperatures. Stoving tem- Product group SILIKOFTAL®

peratures of at least 200°C are necessary Polyester

to ensure complete curing. Silicone-
polyester

Methyl/Phenyl
Crosslinking of silicone resins in the
Silane Resin Intermediate Resins
coating
Figure 4: Resin manufacture at Evonik

In general, various catalysts only have a

limited effect on accelerating the curing
reactions of SILIKOPHEN® and
SILIKOFTAL® resins. The use of large
   
amounts of catalyst to reduce burn-off
temperatures is restricted as problems           
such as low storage stability, gelling or     
increased tendency to yellowing can
occur. For complete curing without addi- Figure 5: Crosslinking reaction of silicone resins
tion of catalyst, we recommend stoving
for 30 minutes at an object temperature
of 250°C (figure 5 shows the crosslinking
reaction of the silicone resins).

Technical Background_Silicone Resins page 137

 Applications of silicone resins and Phenylmethyl silicone resins –
SILIKOPHEN® P resins
­silicone combination resins
Evonik offers a range of phenyl methyl
silicone resins under the trade name
SILIKOPHEN®. The high phenyl group
Guiding formulation for a coating based on SILIKOPHEN® P 80/X content ensures excellent heat resistance
with temperature resistance to 500ºC as well as good compatibility with other
organic resins. As with all phenylmethyl
Component Amount by weight Ingredient
silicone resin coatings, those based on
SILIKOPHEN® P80/X 42.5 Silicone resin
SILIKOPHEN® P resins are thermoplastic.
TEGO® Dispers 670 1.0 Dispersing additive

Bentone® 38 0.3 Rheological additive Illustration 1 gives an overview of the

temperature stability achievable. This
Isobutanol 0.5 Alcohol
depends strongly on the formulation,
Butylglycol acetate 1.2 Glycol ester
­particularly on the pigmentation. While
TEGO® Airex 900 0.5 Deaerator silicone resins with ethyl or propyl groups
Heucodur® 9-100 6.0 Black pigment have low temperature stability, the heat
resistance is distinctly raised if phenyl or
Heucophos® ZPO 6.0 Corrosion protection pigment
methyl groups are incorporated resulting
Mica TM 17.0 Mica
in resins with extraordinary heat resis-
Aerosil® 200 0.5 Pyrogenic silica tance up to 350°C.
Xylene 24.5 Solvent
Such coatings are used mainly in corro-
Total 100.0
sion protection at high temperatures such
Table 2 as car exhausts, smoke stacks, industrial
kilns and combustion chambers (fig. 6).
The property profile of coatings based
on SILIKOPHEN® P resins is strongly
Maximum service temperatures of binders
dependent on the formulation. For heat
Temperature Silicone- Methyl- Phenylmethyl- resistance up to 350°C, formulations
in °C Polyester polyester silicone silicone with heat resistant inorganic colored
700 pigments and titanium dioxide are used.
The guiding formulations in tables 2 and
600
3 give examples for long-term tempera-
500 ture ­levels of 500 and 600°C.
400

300

200

100

Illustration 1 heat resistance as a function of pigmentation continuous heat resistance

page 138 Technical Background_Silicone Resins

SILIKOPHEN® P resins are characterized
by very good pigment wetting. The
films remain fully functional even after
extended exposure to temperatures of
350°C but may gradually lose their gloss.
The maximum thickness of such coatings
should (depending on their pigmentation)
be less than 25 (±5) µm, otherwise sol-
vent blistering can be caused by alcohol
liberated on stoving.
Figure 6: Application of SILIKOPHEN® resins

In addition to this, too high a cured coat-

ing thickness looses flexibility when
exposed to long-term temperatures over
300°C. Flexibility of such high tempera-
ture coatings is obtained by using lamellar Coatings resistant to temperatures in High solid silicone resin SILIKOPHEN® P
fillers such as mica or aluminum flakes. excess of 700°C can be manufactured 80/X or silicone resin emulsion SILIKO-
Care must still be taken to ensure the using ceramic powders. However, the PHEN® P 40/W can satisfy demands for a
same dry coating thickness as above. entire coated surface must be heated reduction in solvent emission. Table 4
above the melting point of the frit. Only gives a guiding formulation for a water-
Primers formulated with zinc dust can be then are permanently bonded, enamel- borne application based on the silicone
used for corrosion-resistant coatings up to like coatings produced by sintering with resin SILIKOPHEN® P 40/W which can
450°C. Coatings which maintain their the siloxane backbone. withstand continuous use at temperatures
protective effect up to 600°C are formu- up to 500°C.
lated using flake inorganic or metallic pig-
ments such as aluminum and mica (table 3).

At temperatures above 350°C, the

organic components of the resin are Guiding formulation for a coating based on SILIKOPHEN® P 80/X
almost completely burned off. Aided by with temperature resistance to 600ºC
sintering, inorganic composites are
Component Amount by weight Ingredient
formed which are very hard and com-
pletely chemically inert but at the same SILIKOPHEN® P80/X 52.0 Silicone resin

time very brittle. Burning off organic TEGO® Airex 900 0.5 Deaerator
groups, especially the phenyl substituents Blanc fixe® N 15.0 Filler
of SILlKOPHEN® P resins, leaves micro-
Aerosil® 200 0.5 Pyrogenic silica
scopically small voids. The resulting
matrix system is so flexible that coatings Stapa® 4 20.0 Aluminum

at a temperature of 600°C can be Xylene 12.0 Solvent

quenched repeatedly with cold water Total 100.0
without cracking.
Table 3

Technical Background_Silicone Resins page 139

 Guiding formulation for a high-temperature resistant coating based on
SILIKOPHEN® P 40/W with temperature resistance to 500°C

Component Amount by weight Ingredient

Water 26.1

TEGO® Dispers 750 W 1.5 Dispersing additive

Metals such as tin can leach out of metal TEGO® Foamex K 3 0.2 Defoamer
cans and lead to formation of gel parti-
Ammonium hydroxide 25% 0.2 Base
cles. Therefore, manufactured paints
should not be stored or packaged in this Heucodur® Schwarz 9-100 8.0 Black pigment

type of container. Heucosil® CTF 5.0 Corrosion protection pigment

Mica TM 14.0 Mica

SILIKOPHEN® P40/W 45.0 Silicone resin

Silicone-polyester resins/
SILIKOFTAL® HT grades Total 100.0

Table 4
Silicone-polyester resins combine the
good properties of silicone resins (tem-
perature resistance, weathering resistance
and low surface tension) with those of
polyesters (low thermoplasticity, high
flexibility and good pigment wetting). greater than 50%, the silicone component ent properties. Evonik offers a wide range
stabilizes the organic component so that of SILIKOFTAL® HT silicone-polyester
By using thermally-stable polyesters, no noticeable yellowing occurs. The prob- grades which are customized for specific
binders can be produced with a continu- able reason for this is that the higher sili- requirements.
ous high temperature resistance of cone content increases the inorganic con-
250°C. tent in the whole polymer thereby The polyester content ensures good
decreasing thermal oxidation. ­pigment wetting. Thus, for example,
With silicone content below 50%, expo- white coatings can be produced with
sure to a temperature of 300°C for three By varying the polyesters and silicone gloss values greater than 90 (20° angle).
hours produces strong yellowing, typical resin intermediates, it is possible to pro- Because of the resistance to yellowing,
of an organic resin. With silicone content duce silicone-polyester resins with differ- very light colors can also be formulated.

page 140 Technical Background_Silicone Resins

 Figure 7: Toaster Figure 8: Frying pan bottom

A further characteristic of coatings based The properties of SILIKOFTAL® HT washer without damage using surfactant-
on SILIKOFTAL® is their low thermoplas- grades are particularly advantageous in containing, strongly-aIkaline cleaning
ticity. As both the silicone and polyester decorative coatings of thermally stressed agents. Resistance of a coating to deter-
portions are strongly crosslinked, the appliances such as toasters, tanning beds, gents is generally determined by the for-
hardness is maintained even at tempera- fan heaters and cookers as well as the mulation, particularly the binder used. It is
tures around 150°C. outer coatings of deep fryers, pots and an important criteria for the quality of sili-
pans (figs. 7 and 8). cone polyesters.
This is important in applications in which
the hot coatings are mechanically stressed Coatings of some household items must The most important properties of differ-
but must be scratch-resistant. be resistant to detergents so that they can ent SILIKOFTAL® HT grades are shown in
withstand frequent cleaning in a dish- table 5.

SILIKOFTAL® grades

Product Silicone
Siliconecontent
content Properties
Properties

retains hardness
retains from
hardness room
from roomtemperature
temperature to 150°C; long-term
to 150°C; long-termheat resistance
heat to 250°C;
resistance to 250°C;
Silikoftal® HTT 80% goodgood detergent
detergentresistance. Currently
resistance. listed FDA
Listed under under175.300
FDA 175.300 insolvent-free
in cured cured solvent-free
resins. resins;
Silikoftal® HTT 80% conforms to BfR.*
very good resistance to yellowing up to 220°C. Listed under FDA 175.300 in cured
Silikoftal® HTS 70% very good resistance
­solvent-free resins.to yellowing up to 220°C. Currently listed under FDA 175.300 in
Silikoftal® HTS 70% cured ­solvent-free resins; conforms to BfR.*
flexible and therefore to a limited extent may be deep drawn. Listed under
Silikoftal® HTF 50% flexible and therefore
FDA 175.300 to a solvent-free
in cured limited extent may be
resins; deep drawn.
conforms to BfR.Currently listed under
Silikoftal® HTF 50% FDA 175.300 in cured solvent-free resins; conforms to BfR.*
high gloss and low thermoplasticity. Listed under
Silikoftal® HTL 50% high FDAgloss and low
175.300 inthermoplasticity.
cured solvent-free Currently
resins. listed under FDA 175.300 in cured solvent-free
Silikoftal® HTL 50% resins; conforms to BfR.*
high gloss, low thermoplasticity, good detergent resistance. Listed under FDA 175.300
Silikoftal® HTL 2 50% high in gloss,
cured low thermoplasticity,
solvent-free resins. good detergent resistance. Currently listed under
Silikoftal® HTL 2 50% FDA 175.300 in cured solvent-free resins; conforms to BfR.*
very good yellowing resistance up to 200°C, very good boiling water resistance.
Silikoftal® HTL 3 30% very goodunder
Listed yellowing resistanceinupcured
FDA 175.300 to 200°C, very good
solvent-free boiling
resins; waterto
conforms resistance.
BfR. Currently
Silikoftal® HTL 3 30% listed under FDA 175.300 in cured solvent-free resins; conforms to BfR.*

Table 5
*Please note that the evaluation regarding suitability for food contact may change, you can find the latest status on our website www.tego.de

Table 5

Technical Background_Silicone Resins page 141

Suitable solvents for silicone-polyester OH content Silicone epoxide combination resins/
resins SILIKOPON® E grades
The free OH-content of SILIKOFTAL®
In unbaked form, silicone-polyesters still resins is not specified. When manufactur- The SILIKOPON® range combines the
have a high OH-content. These polar ing these products, the emphasis is on properties of the widely applicable epox-
groups interact strongly with the ester clarity and viscosity rather than constant ide resins with those of silicone resins.
groups. In the manufacture of the resin, OH-value. SILIKOPON® EW and SILIKOPON® EC
polar solvents are therefore used to are for high-temperature use. Compared
inhibit association and thus maintain a with pure silicone resins (SILIKOPHEN®),
­stable viscosity. If interactions occur, such Stoving conditions and catalysts these silicone/epoxy hybrids offer better
as during cooling, these associations only adhesion to metals as well as better corro-
break up slowly upon warming. In general, the curing reactions of sion protection and chemical resistance.
SILIKOFTAL® resins are accelerated by A typical application is in vehicle exhaust
There is a time delay in physical proper- various catalysts. The use of large amounts coatings where SILIKOPON® EW or
ties such as viscosity and conductivity of catalyst to significantly reduce stoving SILIKOPON® EC is used in primers and a
reaching their final value. When formu- temperatures is not recommended as it SILIKOPHEN® resin in top coats. Such
lating coatings, polar solvents such as can lead to problems such as poor storage two-coat systems are temperature resis-
ketones and esters are preferred to avoid stability, gelling, brittleness and increased tant to 550°C and have excellent corro-
clouding. The use of aliphatic solvents is tendency to ­yellowing. sion resistance.
not recommended.
To achieve full curing without addition of Alongside silicone/epoxy hybrid resins
catalysts, the following conditions are rec- for use at high temperatures, SILIKO-
ommended: PON® EF is a further hybrid for use in
  60 minutes at 220°C topcoats in general industrial and mari-
  30 minutes at 250°C time applications.
  15 minutes at 280°C

page 142 Technical Background_Silicone Resins

 Dynasylan®
SILIKOPON® (3-aminopropyl)-triethoxy-silane

Aliphatic Epoxy
H2O H2N
SILIKOPON® EF is used as a binder for O
ultra high solids applications in corrosion
CH CH3
protection coatings for steel, coatings for R4
wood and concrete and maritime applica-
tions such as biocide-free, easy-to-clean
Alkoxy Silicone resin
coatings particularly above the water line. - ROH RO Si OR
R1

The special feature of the chemical cross- R2 Si OR4 OR

linking of SILIKOPON® EF lies in the dual-
R3 R = Me or Et
cure mechanism at room temperature: the
nucleophilic opening of the epoxide ring
Figure 9: The Dual-Cure Mechanism
(by the amine) and the hydrolysis/con-
densation reaction of the alkoxy groups.
Both reactions occur in situ. The curing
agents are aminosilanes whose amine
groups react with the epoxide groups. The hydrolysis/condensation reaction isocyanate-free, 2-pack formulations with
The three alkoxy groups react in the pres- described in figure 9 can be strongly VOC content less than 250 g/l. In the
ence of water or moisture with the free accelerated by catalysts. These can be tin case of, for example, wood clear coats,
alkoxy group of the silicone resin by compounds or Lewis acids and illustration the VOC can be less than 100 g/l.
hydrolysis/condensation. This “double 2 shows the reduction in drying time The silicone/epoxy resin combination
crosslinking” allows the positive proper- achieved by a tin compound (DOTL) and allows two-coat corrosion protection
ties of organic and inorganic polymers to a Lewis acid (borontrifluoride/ethylamine coatings to be manufactured with SILIKO-
be combined in a new class of binders. complex). PON® EF which can replace the classic
Because of the high crosslink density (see three-coat systems (fig. 10).
fig. 9), these coatings have a high dirt- This binder is suitable for ultra high sol-
repelling effect and are thus very effec- ids, eco-friendly coatings. The particular
tive against graffiti. advantage is that it permits production of

Effect of catalysts on the drying of SILIKOPON® EF

Drying time/hours 0 1 2 3 4 5 6 7 9

SILIKOPON® EF

EF + tin catalyst

EF + Lewis acid

Illustration 2 Touch drying Complete drying

Technical Background_Silicone Resins page 143

 HO OH + HO OH + OCN NCO

1. Polyaddition COOH

PU

OCN NCO
COOH
175μm
2. Neutralization + NHR3
Curing Agent
SILIKOPON®

Epoxy

100μm OCN NCO

- +
COO NHR3
1)
H2O
2)
polyamine
Primer Primer
3. Emulsification - +
COO NHR3
and crosslinking

Steel Steel + +
COO NHR3 COO NHR3
n

Figure 10: Coating structure Figure 11: Synthesis of polyurethane dispersions (schematic)

In addition to the reduced coat thickness The special properties are as follows: In contrast to this commonly-used synthe-
and hence less material needed, cost sav- • quick drying in air sis, Evonik largely replaces the polyester-
ings also accrue because of the reduced • non-stick effect polyol with a silicone base unit, a dihy-
time required for coating. Further advan- • special haptics droxyalkylpolydimethyl siloxane with two
tages arising from the high inorganic con- • hydrophobic terminal OH groups (fig. 12).
tent are good char resistance and high • high flexibility even at low tempera-
abrasion resistance. The high crosslinking tures (-30°C)
CH3
density of coatings based on SILIKOPON® • high elasticity of 300-400%
EF allows this binder to be used in the • good adhesion to flexible substrates HO Si O OH
flooring and industrial plant sectors. • improved abrasion resistance
CH3
n
Figure 12: Dihydroxyalkylpolydimethyl siloxane
Waterborne silicone-modified polyure- Manufacture of SILIKOPUR® 8080
thane dispersions
The synthesis of polyurethane dispersions Applications of SILIKOPUR® 8080
Under the name SILIKOPUR® 8080, usually occurs as the series of consecutive
Evonik offers a waterborne, N-methylpyr- steps shown in figure 12. A diol, dimethy- An application of SILIKOPUR® 8080 is
rolidone-free (NMP-free), silicone-modi- lolpropionic acid and excess isocyanate the coating of leather in, for example,
fied, 1-pack polyurethane dispersion. This are reacted together to form an isocya- shoes, clothing or vehicles. The polyure-
dispersion air-dries at room temperature. nate-terminated prepolymer. After neu- thane formulation increases the slip effect
tralization and chain extension, it is emul- and decreases creaking and squeaking of
sified in water. leather over the long-term.

page 144 Technical Background_Silicone Resins

 non-silicone-modified polyurethane dispersion SILIKOPUR® 8080

Test 1 to 1

sample number
1
load (N)

load (N)
path traversed (mm) path traversed (mm)

Figure 13: Slip properties

Figure 13 compares the slip properties Solid and non-volatile components

with those of a usual waterborne polyure-
thane dispersion.
As with all condensed binders, the amount of solids in
Because of the silicone modification and SILIKOPHEN®, SILIKOPON® and SILIKOFTAL® is not exactly
the anti-stick properties and high flexibil- the same as the amount of non-volatiles. Solids contain low
ity resulting from it, SILIKOPUR® 8080 is molecular resin components and condensed groups which
used in release coatings for EPDM. Fur- are not present in the non-volatile residue after drying.
thermore, the dispersion has good sub-
strate adhesion properties on many other Therefore, the solids content is often a few percent higher
plastics (ABS, GFP, Nornyl, PA, PMMA, than the non-volatiles as determined by DIN 53216. In our
PVC, PC). data sheets, only the amount of non-volatiles is given as this
is the parameter which is important for the user. In contrast,
Illustration 3 shows that a 30% addition the material safety data sheets give the solids content which
of SILIKOPUR® 8080 as co-binder to an is what is important for hazardous goods classification.
acrylic dispersion can improve abrasion
resistance of wood finishes.

Abrasion resistance (CS-17 wheel, 1 kg)

Abrasion (mg) 10 20 30 40

200

150

100

50

Amount of SILIKOPUR® 8080 (%)

Illustration 3 500 abrasion cycles 1,000 abrasion cycles

Technical Background_Silicone Resins page 145

Silica-Nanocomposites
NANOCRYL® – NANOPOX® – NANOPOL®
Because of their special properties, nano- They:
composites are mainly used in coatings •  improve scratch and abrasion resistance
whose characteristics cannot be produced •  improve barrier properties
by conventional means or can only be • improve total transparency of the
achieved by multiple coats. Silica-nano- ­coating
composites are preferred where high •  have no effect on the degree of gloss
scratch and abrasion resistance is needed •  reduce shrinkage during curing
at the same time as transparency. •  reduce tension stress during curing
• improve adhesion on substrates with
Silicon dioxide nanoparticles can be used hydroxyl functions
in the form of liquid composites in many
organic matrices in coating materials. It follows from the above properties that
silica nanoparticles are favored in applica-
tions which require transparency and/or
high abrasion resistance such as high per-
formance coatings or off-shore topcoats.

Manufacture of silica-nanocomposites Starting from water glass (aqueous

sodium silicate solution), spherical silica
Composites can be manufactured from nanoparticles of ca. 20 nm diameter can
silica nanoparticles and organic resins be cultured in an aqueous environment
using a modified sol-gel process. Despite and their growth stopped by wet-chemi-
being 50% w/w filled, they are crystal cal means. These particles then have their
clear. surfaces modified to permit stable trans-
fer into an organic matrix.

Technical Background_Silica-Nanocomposites page 147

Depending on the matrix which will sur- dency to form agglomerates of µm size Use of silica-nanocomposites to
round it, this modification is performed which cannot be re-dispersed. This would ­improve properties
with various agents and can lead to differ- lead to the loss of all the desirable proper-
ent results according to the polarity of the ties of the silica-nanocomposites, such as In addition to the main property of scratch
matrix and silica-nanoparticles. transparency and scratch and abrasion and abrasion resistance while maintaining
resistance. transparency, secondary properties such
In the first purification step, practically all as barrier effects or reduced shrinkage
free ions are removed. In a second step, In principle, a large range of different par- during curing can also be found in impor-
after surface modification with a process- ticle sizes can be produced. An average tant applications.
ing matrix, water is separated. In the third particle diameter of ca. 20 nm has how-
step, the processing matrix is replaced by ever proved optimum for: The particles in the cured film are statisti-
the final matrix. •  optical clarity in coating materials cally distributed. The distribution is, on
•  core/shell ratio average, identical at the surface, in the
Silica-nanoparticles obtained in this way, • high amount of silica nanoparticles in middle and at the bottom.
contain, depending on the matrix, up to the liquid composite
50% silica in nanoparticulate form and •  storage stability
are stable for at least six months. These
products are crystal clear, completely Particle size distribution is very narrow as
transparent and show no sedimentation. a result of process optimization.
Particle size distribution

Free silica-nanoparticles cannot be pre-

pared by this process as, in the absence of
a surrounding matrix, they have a ten-

Silica phase
Route to silica-nanocomposites

Aqueous
Silicate Solution Agglomeration,
gelation, flocculation
particle density

H
Si O
Si
H O

Silica Sol
Surface SNC
modification Low viscosity,
waterclear, 0 20 40 60 80 100
no sedimentation
Matrix exchange particle size [nm]

The silica phase consists of discrete nanospheres (Ø 20 nm) with an

­extremely narrow particle size distribution

page 148 Technical Background_Silica-Nanocomposites