Amino Resins 1
Amino Resins
Hans Diem, BASF Aktiengesellschaft, Ludwigshafen/Rh., Federal Republic of Germany
Günther Matthias, BASF Aktiengesellschaft, Ludwigshafen/Rh., Federal Republic of Germany
1. Introduction . . . . . . . . . . . . . . .
2. Physical Properties . . . . . . . . . . .
3. Chemical Properties . . . . . . . . . .
4. Raw Materials . . . . . . . . . . . . . .
5. Production . . . . . . . . . . . . . . . .
5.1. Principle Aspects . . . . . . . . . . . .
5.1.1. Hydroxymethylation . . . . . . . . . . .
5.1.2. Condensation . . . . . . . . . . . . . . .
5.1.3. Principal Components of an Amino
Resin Solution . . . . . . . . . . . . . . .
5.2. Production Processes . . . . . . . . . .
5.2.1. Batchwise Production . . . . . . . . . .
5.2.2. Continuous Production . . . . . . . . .
5.2.3. Production of Special Products and
Foams . . . . . . . . . . . . . . . . . . . .
6. Environmental Protection . . . . . .
7. Types of Resins
and Their Properties . . . . . . . . . .
7.1. Urea Resins (UF Resins) . . . . . . .
1. Introduction
Amino resins are condensates formed when car-
bonyl compounds react with compounds con-
taining amino, imino, or amide groups, liber-
ating water. Before they have hardened, these
products consist principally of oligomers, which
are also called prepolymers.
A very large number of carbonyl- and
nitrogen-containing compounds yield conden-
sates of relatively low molecular weight. The
type of interaction is determined by the
functional groups. Among such compounds,
formaldehyde, urea, and melamine have become
the most important, especially because of their
relatively low prices. These products are ob-
tained by large-scale production in modern in-
dustrial plants. The amino resins offer technical
advantages in many applications.
History. The history of amino resins began
with the synthesis of the two main raw mate-
rials, urea and formaldehyde; the former was
prepared by F. Wöhler in 1824, and the latter

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a02 115
1 7.1.1. Pure Urea – Formaldehyde Resins . . 13
2 7.1.2. Mixed Condensates . . . . . . . . . . . 14
2 7.1.3. Condensation of Urea with Other
3 Aldehydes . . . . . . . . . . . . . . . . . 14
5 7.1.4. Resins from Urea Derivatives . . . . . 14
5 7.1.5. Modified Urea Resins . . . . . . . . . . 15
6 7.2. Melamine Resins . . . . . . . . . . . . 17
6 7.2.1. Unmodified Melamine Resins . . . . . 17
7.2.2. Modified Melamine Resins . . . . . . . 17
7 7.3. Urethane Resins . . . . . . . . . . . . . 18
7 7.4. Cyanamide and Dicyanodiamide
7 Resins . . . . . . . . . . . . . . . . . . . . 18
10 7.5. Sulfonamide Resins . . . . . . . . . . . 18
7.6. Aniline Resins . . . . . . . . . . . . . . 19
11 8. Analysis . . . . . . . . . . . . . . . . . . 19
12 9. Storage and Shipment . . . . . . . . . 20
10. Uses . . . . . . . . . . . . . . . . . . . . . 21
13 11. Economic Aspects . . . . . . . . . . . . 26
13 12. References . . . . . . . . . . . . . . . . . 27
by A. Butlerov in 1859. However, the first in-
vestigations of urea – formaldehyde (UF) resins
were not carried out until about 1880. The first
reaction products were reported by B. Tollens
(1884) and C. Goldschmidt (1887), and the ba-
sic chemistry of the amino resins was established
about 1908 [14].
F. Pollack and K. Ripper (1921) synthe-
sized a clear transparent material, which they
called “Pollopas.” This product never became
commercially important, but it did give rise to
a number of experiments. The first commer-
cial products, manufactured by E. C. Rossiter
of British Cyanides Co. in 1924 and 1925, led
to molding materials still in use today.
The melamine resins were introduced in Ger-
many by Henkel in 1935 [15]. Their properties
are similar to those of the urea – formaldehyde
resins, but the resins are of higher quality. For ex-
ample, they are chemically stable after the resin
has hardened and become insoluble.
An ever-increasing number of mixtures of
urea – formaldehyde and melamine – formalde-
hyde resins are produced for the most diverse
2 Amino Resins
uses. Lower costs and the better performance of
the products made from these mixtures account
for their popularity.
Amino resins find their major use as ad-
hesives. They are used in the production of
plywood, waferboard, strandboard, and particle
board. Other types are employed for the produc-
tion of laminated beams and parquet flooring,
and for furniture assembly. Amino resins are also
used to strengthen paper, to produce molding
compounds and the flexible backing of carpets,
as leather auxiliaries and soil conditioners, and
for protective surface coatings.
2. Physical Properties
Amino resins are available commercially as con-
centrated solutions or solids, e.g. powders. The
solutions generally contain water as a solvent,
but in the surface-coating resins the solvents are
alcohols. The solutions range from colorless and
clear to milky and cloudy and are tacky to the
touch. Their viscosities are substantially higher
than that of water, from 20 to 70000 mPa · s –
in general from 200 to 2000 mPa · s – measured
at 20 ◦ C. The amino resins can be odorless or,
depending on the content of free formaldehyde,
have a more or less sharp odor. The densities of
the solutions at the commercially available con-
centrations of 55 – 80 % solids are from 1.23 to
1.31 g/cm3 . An important property of the resins
is the amount of water that can be added with-
out precipitating solids. At relatively low tem-
peratures, i.e., below about 20 ◦ C, pronounced
cloudiness and an unusually large increase in
viscosity are observed in many cases.
Some resin solutions exhibit the phenomenon
of pseudoplasticity (thixotropy), which may or
may not be desirable. Thixotropy means that
the viscosity decreases as the shearing force in-
creases [16], [17].
In powder form amino resins are white. In the
spray-dried, commercially available form they
have a particle size generally of 15 – 70 µm, but
always < 200 µm. This particle size is a result
of the spray-drying process [18]. The bulk den-
sity of the commercially available products is
0.5 – 0.8 kg/L. The powder resins dissolve in wa-
ter to give milky liquids. Flourlike additives can
be mixed with some resins, which then assume
the color of the additive to a greater or lesser
extent.
3. Chemical Properties
Even when they are prepared from only two
components, the amino resins are mixtures of
various substances. For example, in the case
of urea – formaldehyde resins the major compo-
nents of the mixture are various hydroxymethyl
compounds and oligomers composed of differ-
ent combinations of basic units and substituted
basic units. These oligomers are of different
sizes. As an approximation, the basic unit can
be described as methylene – urea (1), which can
carry various substituents at the nitrogen atoms:
Hence, it is not possible to attribute specific
chemical properties to these substances, as in the
case of a pure compound.
However, some chemical properties are com-
mon to all or most amino resins.
The chemical properties given below are im-
portant with regard to processing the resins. The
equations given for urea – formaldehyde also ap-
ply in principle to other reactants employed for
these classes of products.
– Formaldehyde is slowly split off from hy-
droxymethyl compounds and undergoes ad-
dition reactions with other amino groups in
accordance with the equilibrium equation
[19], [20]:
H2 N–CO–NH2 + CH2 O
H2 N–CO–NH–CH2 OH
– Hydroxymethyl compounds undergo slow
condensation in the absence of heat or
react with urea to give methylene com-
pounds, such as methylene – diurea or meth-
ylene – oligourea:
H2 N–CO–NH–CH2 OH + H2 N–CO–NH2 −→
H2 N–CO–NH–CH2 –NH–CO–NH2 + H2 O
2 H2 N–CO–NH–CH2 OH −→
H2 N–CO–NH–CH2 –NH–CO–NH2 + CH2 O + H2 O

These reactions are responsible for the grad-
ual increase in viscosity that amino resins
undergo during storage [21].
– It is assumed that bis-methylene – urea ethers
(2) are formed [13, p. 324], [20], [22], but
amino resin solutions contain only small
amounts of these ethers. Under certain pro-
duction conditions cyclic ethers, so-called
urones (3), also occur.
– Amino resin solutions generally are rendered
slightly alkaline, i.e., pH 8 – 9, in order to sta-
bilize them, but the pH slowly decreases as
formic acid is formed.
These reactions, especially condensation
with the formation of methylene bridges, are
accelerated by acid catalysts and elevated tem-
peratures. Hence, in processing amino resins,
acids or acid-forming substances are impor-
tant as hardeners that accelerate the con-
densation. Alkali-catalyzed condensation [13,
pp. 331 – 332], [23] is of no practical impor-
tance.
The hydroxymethyl groups can be converted
with alcohols to the corresponding ethers. This
reaction is utilized in surface-coating resins and
to a lesser extent in glues for particle board and
in textile and paper auxiliaries.
The free formaldehyde, which is present in
concentrations of from 0.1 % to about 2 %,
is of practical importance in many cases be-
cause it reacts with ammonium salts of acids to
give hexamethylenetetramine and the free acid,
which acts as a hardener.
Resin powders also condense over time to
give relatively high molecular mass products,
but in this case the reaction is slower by a factor
of at least five.
4. Raw Materials
The principal carbonyl component is formalde-
hyde, but furfural and glyoxal are employed also.
Amino Resins 3
Only formaldehyde is important in industrial
production. Other aldehydes are employed, but
these play a very minor role.
The most important amine-containing com-
ponents are urea and melamine, but thiourea,
guanidine, cyanamide, and dicyanodiamide, and
to a lesser extent acid amides, guanamines, and
aniline, are employed also. Further components
include the derivatives of these compounds, e.g.,
substituted ureas.
Relevant information on raw materials used
to produce amino resins can be found in [1,
pp. 3 – 85].
Products that are added in relatively small
amounts to effect slight but often important
changes in the properties are called modifiers.
These include alcohols, amines, aminoalcohols,
and a very large variety of other organic and in-
organic substances [1, pp. 7 – 122].
Finally, it should also be mentioned that in-
ert inorganic salts sometimes are added during
the production or processing of glue resins [8,
p. 34], [24], [25].
Formaldehyde, CH2 O, M r 30.03, [50-00-0]
(production and properties → Formaldehyde).
In the production of amino resins, formalde-
hyde is used either in the form of solid
paraformaldehyde, in aqueous solution, or as a
urea – formaldehyde precondensate containing
from 4 to 5 mol of formaldehyde per mole of
urea. Paraformaldehyde is a mixture of hydrated
polyoxymethylene molecules, with a degree of
polymerization of 6 – 100 units. The melting
point ranges from 120 to 170 ◦ C, depending on
the molecular mass.
HO – [CH2 O]n – H n = 6 – 100
The most frequently used commercial form
is a 30 – 55 % aqueous solution of formalde-
hyde. These solutions are clear, caustic, and in-
flammable, have a sharp odor, and are infinitely
miscible with water. Formaldehyde is present in
aqueous solutions predominantly as the hydrate
(HO–CH2 –OH), which is in equilibrium with its
oligomers:
n CH2 (OH)2
HO(CH2 O)n H + (n − 1) H2 O
Depending on the method of production, the so-
lutions are contaminated with a few hundredths
of a percent of formic acid and from 0.5 to 2 % of
4 Amino Resins
methanol. The content of formic acid and meth-
anol increases during storage, as a result of the
Cannizzaro reaction:
2 CH2 O + H2 O −→ HCOOH + CH3 OH
Moreover, on long-term storage at low tempera-
tures, paraformaldehyde separates as a hazy sus-
pension or a precipitate. This process is retarded
by the addition of stabilizers, e.g., up to 12 % of
methanol or triazine derivatives.
Depending on the concentration and
the methanol content, the flash point is
about 60 – 85 ◦ C. The regulations governing
flammable liquids do not apply to aqueous
formaldehyde solutions.
Formaldehyde solutions can be stored and
transported in containers made of stainless
steel, aluminum, polyester resin, or appropri-
ately lined iron.
Finally, aqueous solutions of urea – form-
aldehyde precondensates also are employed.
Commercially available solutions contain from
70 to 80 % of the active ingredients, cal-
culated as urea and formaldehyde. The mo-
lar ratio of formaldehyde to urea ranges from
4 : 1 to 5 : 1, and the mass ratio is therefore
2 : 1 to 2.5 : 1. These solutions are substan-
tially more resistant to polymer precipitation
than are pure formaldehyde solutions. In the
urea – formaldehyde precondensates, the major
part of the formaldehyde is present in the form
of urea – hydroxymethyl compounds, a smaller
part as formaldehyde or its oligomers in the hy-
drated form, and a very small part as conden-
sates. In this last case, the urea molecules are
linked mainly via methylene bridges.
Biologic Effect. The maximum allowable con-
centration (MAK value) recommended by the
Senate Committee of the Deutsche Forschungs-
gemeinschaft (German Research Organization)
in the Federal Republic of Germany is 1 ppm.
The corresponding values for the United States
of America (given by OSHA) and Japan are
3 ppm and 2 ppm, respectively. At present,
regulations vary from country to country
(→ Formaldehyde, Chap. 10.).
Other Aldehydes. Other aldehydes play a
minor role. Glyoxal [107-22-2] is available com-
mercially in the form of 30 – 40 % aqueous so-
lutions. The purity is 97 – 99 %. Depending on
the production method, the solutions contain
0.1 – 0.2 % acid constituents. The color number
should have a maximum value of 15 (APHA).
Glyoxal is hydrated in the aqueous solution.
Urea [57-13-6], carbamide, diamide of car-
bonic acid, H2 NCONH2 , M r 60.06 (→ Urea).
Urea is available commercially as a white
crystalline product or as prills. For amino resin
production, a technical-grade product is usually
adequate.
It should be noted that fertilizer urea fre-
quently is contaminated with ammonium salts,
and these may act as hardeners and cause the
glue mixture to solidify even in the production
stage. Furthermore, the prilled urea can be mixed
with sulfur or formaldehyde to keep it free flow-
ing. Sulfur-coated urea is not recommended for
resin production. The formaldehyde forms insol-
uble condensates on the surface of the prills, and
these condensates can lead to a slight cloudiness
when the prills are dissolved.
The dissolution of urea in water is an en-
dothermic process. The enthalpy of solution
(∆H) is + 257.5 J/g, measured at 10 ◦ C in a 20-
fold amount of water.
In the production of amino resins, urea is
employed in solid form, in solution, or as a
urea – formaldehyde precondensate.
Thiourea [62-56-6], thiocarbamide,
NH2 CSNH2 , M r 76.12 (→ Thiourea).
Thiourea is a relatively expensive raw mate-
rial and is therefore not very important indus-
trially. Apart from its use in special products, it
serves only as a modifier, for example, in im-
pregnating resins. Thiourea improves the resin
properties, e.g., hardness, surface gloss, and wa-
ter resistance.
The melting point of thiourea is 180 ◦ C. Its
solubility in water is 9 % at 100 ◦ C, substantially
lower than that of urea.
Substituted Ureas. Cyclic ethylene ureas
and propylene ureas (2-oxoimidazolidine and
2-oxohexahydropyrimidine) are employed for
the preparation of textile auxiliaries. Because of
their high price and their limited ability to form
condensates, they are not used in large amounts
for any other purposes.

Melamine [108-78-1], 2,4,6-triamino-
1,3,5-triazine, cyanurotriamide, M r 126.13
(→ Melamine and Guanamines). Melamine (4)
is a white powder that sublimes on heating.
The particle diameter depends on the produc-
tion process and varies from 5 to 300 µm. The
rate of solubility in formaldehyde solutions de-
pends on the particle size and is an important
parameter given in the information leaflets of
melamine producers. The color number of a
50 % melamine – formaldehyde solution may
not exceed 20 (APHA). This is important with
respect to raw materials for surface coatings and
to impregnating resins.
Melamine derivatives, e.g., benzoguanamine
(5), are employed as modifiers.
Modifiers. A very large number of additives
from all areas of organic and inorganic chem-
istry have been used to modify amino resins;
most of these additives are no longer impor-
tant [1, pp. 107 – 122]. Aliphatic alcohols, sug-
ars, polysaccharides, and caprolactam are addi-
tives for special purposes and are still used today.
5. Production
5.1. Principle Aspects
Amino resin production consists of two
stages: hydroxymethylation and condensation.
Depending on the reaction conditions, hy-
droxymethylation is accompanied to a greater
or lesser extent by condensation. The following
equations illustrate the process in a simple case,
for example, for formaldehyde plus urea:
Hydroxymethylation:
NH2 CONH2 + 2 CH2 O
HOCH2 –NHCONH–CH2 OH
Condensation:
HOCH2 –NHCONH–CH2 OH + NH2 CONH2 −→
HOCH2 –NHCONH–CH2 –NHCONH2 + H2 O
Amino Resins 5
Further condensation leads to longer chains of
the basic unit
Hydroxymethylation is carried out in a
slightly alkaline or slightly acidic medium,
whereas the condensation requires a more
strongly acidic solution. The process for the pro-
duction of the resin is continued until the re-
sulting product is an oligomeric mixture that is
still soluble or fusible. It is protected against fur-
ther condensation by rendering the medium al-
kaline. Condensation of the resin by means of
acid catalysis, i.e., cross-linking to give a sub-
stantially infusible product, is not carried out un-
til the resin is put to use. This process is called
curing. However, free hydroxymethyl groups are
present even in this state.
The monomolecular and hydroxymethyl
compounds with low degrees of polymerization
and up to six urea – formaldehyde units are virtu-
ally all known and can be prepared in pure form
[1, p. 20]. Aqueous solutions of the oligomers
with low degrees of polymerization do not have
a sufficiently long shelf life. Only when the con-
centrations of hydroxymethyl and NH2 groups
are reduced by partial condensation or when the
products are present in solid form do they pos-
sess an industrially useful shelf life, i.e., several
weeks or more.
Condensations carried out in an excess of an
alcohol, such as methanol or butanol, with the
addition of acid and removal of water as nec-
essary, produce curable etherified amino resins.
These are soluble in nonaqueous solvents and
can be mixed with alkyd resins, epoxy resins,
etc. They are used as starting materials in the
production of surface coatings.
Resin glues based on urea, melamine, or both
have been subjected to partial etherification to
stabilize them against further condensation [26–
28].
Preventing the resins from solidifying during
the production process and selectively achieving
certain properties – such as long shelf life, low
formaldehyde content, strength, and resistance
to swelling of particle board after curing – are the
basic difficulties encountered. Frequently, novel
properties are required on short notice by the
market.
6 Amino Resins
5.1.1. Hydroxymethylation
Hydroxymethylation can be carried out using
either alkaline or acid catalysis, but the for-
mer is faster. The reaction mechanisms in acidic
and alkaline media differ. In acids, condensa-
tion takes place at the same time. Hence, hy-
droxymethylation is carried out industrially in
an alkaline or slightly acidic solution.
In hydroxymethylation, a semiaminal bond is
formed:
This is cleaved readily, and hy-
droxymethylation reactions are reversible and
establish an equilibrium [32]. Although mono-,
di-, and trihydroxymethylurea are formed and
isolated easily, tetrahydroxymethylurea is virtu-
ally nonexistent in aqueous solution. The com-
plete hydroxymethylation of all amino groups
to form hexahydroxymethylmelamine can be
carried out readily. The hydroxymethylation of
urea is slightly exothermic:
H2 N-CO-NH2 + CH2 O
H2 N-CO-NH-CH2 OH
∆H = - 23 kJ/mol
The ∆H data given in the literature fluctuate
about this value by ± 5 kJ/mol. The enthalpy of
hydroxymethylation of melamine, relative to the
amount of formaldehyde, is − 15 kJ/mol [29],
[30].
Reaction rates have been measured fre-
quently, but they are sensitive to many parame-
ters [19], [29].
Industrial processes produce variable mix-
tures of oligomers with mixed repeat units,
so the overall reaction rate is also variable
and cannot be defined. Moreover, the im-
portant resin properties have not been cor-
related with the individual reaction rates. In
general, the hydroxymethylation rate increases
with increased concentration, temperature, and
pH. Substituents also have an effect; adjacent
electron-withdrawing groups reduce the reac-
tion rate, as do bulky substituents.
5.1.2. Condensation
The condensation is catalyzed by acids. Cataly-
sis by strong alkalis has been described also, but
the resulting amino resins are not important in-
dustrially [23]. The condensation can take place
by the following routes:
Although the presence of methylene com-
pounds in amino resins can be established unam-
biguously by means of 13 C NMR, bis(ureameth-
ylene) ethers can be detected only by an indirect
procedure [31]. Carbon-13 NMR spectroscopy
permits the elucidation of many of the structures
but does not distinguish between the C atoms
shown in boldface in (6) and (7), although their
third nearest neighbors are different.
This problem also occurs in the case of
melamine resins [33].
The methylene bonds between two urea
molecules are very stable and can be hydrolyzed
only by strong acids at elevated temperatures
(see Chap. 8). The condensation reaction is
slightly exothermic; the enthalpy is − 28 kJ/mol
[29]. The stability of the methylene-ether bond
is between that of the hydroxymethyl bond and
that of the methylene bond.
It is impossible to give a single reac-
tion rate for the condensation process because
there are many different starting materials (hy-
droxymethyl compounds) and many end prod-
ucts (methylene compounds).
The type of solvent also has an effect on the
condensation rate [34]. The dependence of the
reactivity of hydroxymethyl compounds on the
chemical composition of the amino compounds
can be interpreted on the basis of several quali-
tative rules [35].

5.1.3. Principal Components of an Amino
Resin Solution
It is possible to identify the most important struc-
tural moieties of the oligomers in amino resin
solutions by means of 1 H and 13 C NMR spec-
troscopy [22], [31], [36].
The hydrates of the formaldehyde oligomers
HO(CH2 O)n H, where n is about 5, can be de-
tected along with the following hydroxymethyl
structures:
Ethers, such as hydroxymethyl methyl ether,
also can be identified in the spectrum by distin-
guishing the C atoms of the parent alcohol.
Finally, the structures (8) and (9) and ring
compounds, including cyclic ethers of the urone
type, also appear.
In a typical particle board glue, the 13 C NMR
spectrum might show, for example, the follow-
ing distribution of the carbon atoms of the orig-
inal formaldehyde (mole fractions):
formaldehyde 0.03
hydroxymethyl compounds 0.72
methylene compounds 0.15
cyclic compounds 0.10
5.2. Production Processes
Amino resins usually are prepared in 5 – 20 m3
batches. However, continuous processes are em-
ployed also, particularly for the production of
resin glues. The patent literature describes pro-
cesses where a particular stage is operated con-
tinuously while other stages are operated batch-
wise.
Because the reaction rate and the composi-
tion of the end product are influenced by a large
Amino Resins 7
number of parameters, the reaction must be con-
trolled carefully. Important reaction parameters
are:
1) purity or composition of the starting materi-
als
2) molar ratio in each of the reaction stages
3) type and amount of modifier
4) reactant concentrations
5) the pH value at each stage of the reaction
6) temperature at each stage of the reaction
7) type and concentration of catalyst
8) amount of buffer salt
9) reaction time in each stage
The large number of reaction parameters and
resultant adaptations of the process lead to a very
extensive body of relevant literature, particularly
patent literature. Only the important processes
are described here, but a comprehensive review
can be found in [1, pp. 101 – 105].
5.2.1. Batchwise Production
The batchwise procedure is the most widely used
method for the industrial production of amino
resins, but it has the disadvantage of a rela-
tively small production capacity. Nevertheless,
this process permits an extensive variety of prod-
ucts and frequent changes of product.
The reactions are carried out in stirred ket-
tles, in two or more stages, at 70 – 100 ◦ C. In
the first stage, which is carried out in a slightly
acidic to alkaline solution, the principal reaction
is hydroxymethylation. In subsequent stages, the
condensation is carried out, water is split off, and
higher molecular weight products of increasing
viscosity are obtained. The duration of the con-
densation depends on the properties desired in
the product. In general, the products are concen-
trated to 60 – 70 % aqueous solutions by evapo-
ration. The starting materials, urea or melamine,
are employed in powder form. Urea also can
be used in solution. Formaldehyde is employed
as a 37 – 55 % aqueous solution. In a few spe-
cial cases, formaldehyde is used in the solid
form, paraformaldehyde. Finally, it is possible
to employ urea – formaldehyde precondensates
in concentrations of not more than 80 % by mass
of the active ingredients.
Figure 1 shows a diagram of a plant for the
batchwise production of aqueous solutions.
8 Amino Resins
Figure 1. Plant for the batchwise production of aqueous amino resin solutions
a) Stirred kettle; b) Raw material feed; c) Reflux condenser; d) Temporary container; e) Pump; f) Vaporizer; g) Container for
finished product; h) Condenser; i) Vacuum pump; k) Vessel for condensed vapors; l) Cooler
Aqueous Solutions. The reactor consists of
a kettle equipped with heating and cooling de-
vices, a stirrer, inlets for feeding in the raw ma-
terials and for measuring devices, a valve at the
bottom for emptying the kettle, and a manhole
for cleaning.
The material used is mainly stainless steel,
material No. St. 1.4541 or St. 1.4571. Internal
coils or external, welded-on, semicircular pipes
provide for heating with steam or cooling with
cold water. Stirring is carried out by means of a
powerful unit consisting of disk or anchor stir-
rers. Nozzles are welded on in order to meter in
the raw materials and to permit measurement of
the temperature and pH.
When the condensation is complete, the prod-
uct is evaporated. This is carried out in the stirred
kettle, or more economically in a single- or mul-
tistage tubular vaporizer, with the pressure re-
duced to protect the resin. The quality of the
resin is then compared to its specifications and
it is discharged into a storage container.
The product tanks and the pipelines can be
of aluminum or steel because the medium is
slightly alkaline. It is advantageous to provide
lined iron tanks.
A typical, simple resin glue for particle board
production is made as follows [37], [38]: 60
parts (by mass) of solid urea are introduced
into 158 parts of a 40 % formaldehyde solution
that has been rendered neutral. The mixture is
kept at 80 ◦ C for 10 min, during which time hy-
droxymethylation takes place. The pH is then
brought to 4 – 5 by adding a 10 % formic acid
solution. The condensation causes the tempera-
ture to rise to 97 – 100 ◦ C within a few minutes.
This temperature is maintained for about 30 min
or until a mixture of 1 part of reaction solution
and 5 parts of water gives a white precipitate at
15 ◦ C (sharp endpoint). The reaction mixture is
then brought to pH 7 with a 25 % sodium hydrox-
ide solution. This terminates the condensation.
A further 16 parts (by mass) of urea are then
added, so that the molar ratio of formaldehyde
to urea in the end product is 1.65. The resulting
solution has a solids content of 51 %. The resin
solution is evaporated under reduced pressure to
the commercial concentration of 66 %.
This 66 % solution of amino resin forms
a milky solution and has a viscosity of
about 500 mPa · s (at 20 ◦ C) and a density of
1.290 g/cm3 .
A typical resin for the impregnation of paper
webs used in producing decorative laminates can
be made as follows [12, p. 258]:
126 parts (by mass) of melamine are intro-
duced into a stirred solution of 120 parts of a
40 % formaldehyde solution and 70 parts of

Figure 2. Plant for the production of amino resin powders by spray drying [18, p. 501]
a) Starting material feed; b) Stirred kettle; c) Reflux condenser; d) Temporary container; e) Pump; f) Spray drier; g) Blower;
h) Air heater; i) Filter; j) Mixing bin; k) Vibrating sieve
water at room temperature. The reaction mix-
ture is brought to pH 9 by adding aqueous
sodium hydroxide solution and is then heated
very rapidly, i.e., in 20 – 30 min for an industrial-
scale mixture, to a temperature of 100 ◦ C. After
the melamine has dissolved, a process that takes
place exothermally, sodium hydroxide solution
is added continuously to keep the pH value of
the reaction mixture at 8.5 – 8.8 throughout the
condensation. Condensation is carried out, with
gentle refluxing and stirring, until the reaction
mixture is compatible with water when mixed
in the ratio 1 : 1.5. This is the case when a sam-
ple of the reaction mixture exhibits slight cloudi-
ness when water, at 1.5 times the amount of so-
lution, is added at 20 ◦ C. The reaction solution
is then cooled rapidly and brought to pH 9.5 – 10
at room temperature by the addition of sodium
hydroxide solution. The resultant impregnating
resin solution has a solids content of about 55 %
and is usually clear.
Amino Resin Powders. In the production
of amino resin powders, an aqueous resin so-
lution is first produced (Fig. 2) and then fed into
a spray drier, where it is atomized by a spray
disk or nozzle. The resultant droplets are dried
in the stream of hot gas produced by heating air
indirectly in a heat exchanger or by mixing hot
exhaust gas with air. The powder is collected in
Amino Resins 9
a tower and in cyclone separators or filters. It
passes via a vibrating sieve into a mixing bin
and then pours into sacks or drums.
Etherified Products Containing Solvent.
Products of this type, which are used as starting
materials for making surface coatings, can be
produced in a reactor like that described in the
production of aqueous solutions of amino resins
(Fig. 3). The reactor must be equipped with a
sufficiently large heat exchanger to vaporize the
mixture of water and excess alcohol, e.g., bu-
tanol. Downstream from the heat exchanger is
a water separator. The separated aqueous phase
still contains from 1 to 2 % formaldehyde and
20 % alcohol and therefore must be worked up.
At the appropriate alcohol content, this solvent
phase is recycled to the production process.
A butylated melamine – formaldehyde resin
for surface coatings can be produced in the fol-
lowing way [11, p. 69]:
60 parts (by mass) of melamine, 60 parts (by
mass) of formaldehyde (calculated at 100 %)
in the form of a 40 % aqueous solution, and
220 parts (by mass) of butanol are refluxed for
30 min in a stirred kettle equipped for heating.
Distillation is then carried out until water no
longer evaporates. Then a further 20 – 25 parts
(by mass) of anhydrous butanol are distilled.
10 Amino Resins
The mixture is cooled, the resin content is de-
termined, and the concentration is then brought
to 50 % with butanol.
5.2.2. Continuous Production
The continuous industrial production of amino
resins was begun in order to meet rising demand.
The disadvantages of continuous production are
that the amount produced per unit time in a par-
ticular plant can vary only within relatively nar-
row limits because prolonged residence under
otherwise constant conditions increases the pro-
portion of molecules with high degrees of con-
densation. Changing product is not simple ei-
ther. If the plant is not cleaned out beforehand,
a product having a composition between the old
product and the new will be formed for a time.
For this reason, the continuous production pro-
cess is employed where the variety of products
is restricted to a relatively narrow range. On the
other hand, continuous procedures give a very
uniform product quality.
Figure 3.Plant for the batchwise production of etherified
amino resins
a) Raw material feed; b) Stirred kettle; c) Condenser; d) Vac-
uum pump; e) Separating vessel (water separator); f) Prod-
uct vessel; g) Pump
The patent literature describes a large number
of continuous processes. They differ only in pro-
cess technology for the product flow. In general,
the differences include variations in the tem-
perature, pH, concentration, or modifiers. The
process and product flow otherwise remain un-
changed. In many cases the publications only de-
scribe laboratory- or pilot-scale plants that have
not been scaled up for industrial use. Of the con-
tinuous processes that have been described, only
those with basic differences in type are discussed
here.
Aqueous Solutions. The apparatuses em-
ployed for the continuous production of aqueous
amino resin solutions are tube reactors, stirred
kettle cascades, or combinations of the two. The
danger of incrustation by highly condensed, in-
soluble products is greater in the continuous pro-
cess than in the batch process. In the latter, the
residues are dissolved by fresh resin solutions;
this is not the case in the continuous process be-
cause very little backmixing occurs.
A continuous two-reactor process was de-
scribed by the Girdler Corp., United States of
America, in 1943 [39]. The reactants were mixed
thoroughly in the first reactor and heated to about
150 ◦ C under pressure. In the second stage, the
solution under pressure was maintained at this
temperature and condensation was carried out.
The pressure of the reactor was then released,
with the result that volatile constituents, espe-
cially water, escaped from the resin and the so-
lution cooled.
According to a 1949 patent granted to Sher-
wood Paints, UK, the reaction is carried out in a
packed column [40] and water vapor is expelled
by means of a countercurrent gas stream.
A process of Allied Chemical Corp., United
States of America (1951), operates in a simi-
lar manner and employs a tubular coil as the
reactor [41]. The resin solution is subsequently
evaporated. Another process of Allied Chemi-
cal Corp. is carried out under pressure, using
injected steam (1952) [42].
According to an application by Spumalit-
Anstalt, Liechtenstein, the starting materials
are passed over a solid catalyst (polycar-
bamide resin) under a pressure of 400 kPa at
140 – 150 ◦ C to form the resin [43].
A process of Rütgerswerke, Germany, from
1955 also uses a fixed-bed catalyst, an ion ex-
changer [44]. The resins obtained are used as
starting materials for making molding com-
pounds.

A Swedish application by Skanska Attifab-
riken AB from 1955 describes a process in which
starting materials are heated separately and then
sprayed into a chamber to undergo partial con-
densation [45]; the reaction is completed in an-
other chamber. The advantage claimed is that
none of the final products participates in the ini-
tial stages of the condensation.
An application by Du Pont, United States
of America, in 1956, describes a con-
tinuous process for producing etherified
formaldehyde – urea resins [46]. The stepwise
reaction takes place in a cascade of two to four
stirred kettles. The free alcohols (e.g., butanol,
isobutanol, and others) are distilled in the last
stage, and some of them are recycled.
In a Meissner process from 1966, the hy-
droxymethylation stage is carried out continu-
ously and the subsequent condensation stage is
operated batchwise [47]. The continuously flow-
ing product stream from the first stage passes
through a stirred kettle, which is one of a large
number of kettles, so that the product flow need
not be interrupted.
Other continuous processes have been
worked out by Rheinpreussen AG [48] and the
St. Regis Paper Co. [49], but these processes
predominantly relate to phenoplasts.
A BASF process (1971) is shown diagram-
matically in Figure 4 [50]. The reaction is car-
ried out in a series of three or more stirred kettles.
At the beginning of the cascade predominantly
hydroxymethylation takes place. Condensation
occurs later in the cascade. The reaction is ter-
minated in the last section by the addition of
sodium hydroxide solution. The resin solution
passes into a temporary container and is sub-
sequently evaporated under reduced pressure in
a single- or multi-stage vaporizer. The vapors,
containing about 2 % formaldehyde, are worked
up and the effluent is discharged for treatment.
The end product is cooled and pumped into a
tank.
Other cascade processes have been described
in applications of SIR, Milano, Italy, (1972) [51]
and Montedison (1980) [52].
Finally, mention should be made of the pro-
cess in which formaldehyde is absorbed directly
in urea solutions to produce highly concentrated,
formaldehyde-rich solutions that are used as
starting materials for glue resins. Examples of
conventional commercial products are Kaurit-
Amino Resins 11
Konzentrat 244 fl. or 255 fl. (BASF), Formurea
80 (Montedison), and Saruform 80 (Chemische
Werke Saar Lothringen).
Stamicarbon [53] and American Cyanamid
[54] have described the continuous production
of concentrated, formaldehyde-rich melamine –
formaldehyde solutions. These too can be used
as starting materials for amino resins.
Resins in Powdered Form. Resins in pow-
dered form also can be produced by a continu-
ous procedure if the spray solutions, which in
general are produced batchwise, are fed contin-
uously from a temporary container into a spray
tower [18].
5.2.3. Production of Special Products and
Foams
In addition to impregnating resins, special prod-
ucts include foamed resins and resins for pa-
per auxiliaries, label adhesives, concrete lique-
fiers, leather auxiliaries, carpet coatings, micro-
capsules, etc. Because of the relatively small in-
dividual amounts and the large variety of prod-
ucts, these resins are produced virtually always
in batches. The principle of the production is the
same as that for the manufacture of resin glues.
The proprietary know-how relates to modifiers
and small but important variations in the manner
in which the process is carried out.
The foamed resins (→ Foamed Plastics) are
an interesting type of amino resin. They are
used to produce solid foams, which have a wide
variety of applications. The productions of the
foamed resin solution and the end product, i.e.,
the foam, are discussed together.
In 1927, E. C. Bayer discovered that porous,
heat-insulating materials are obtained if a foam
or a foam-forming substance is added to a glue
solution and the mixture is foamed and allowed
to harden. In 1933, a process for the production
of a foamed urea formaldehyde resin was devel-
oped by I. G. Farbenindustrie. In this process, a
foaming agent and air were used to produce a
primary foam that itself contained the acid, e.g.,
phosphoric acid, for curing the amino resin. Cur-
ing begins after a few seconds and is complete
after 12 – 24 h at room temperature. After dry-
ing, the foamed urea formaldehyde resins have
12 Amino Resins
Figure 4. Plant for the continuous production of aqueous amino resin solutions [50]
a) Starting material feeds; b) Stirred kettle; c) Reflux condenser; d) Flare; e) Temporary container; f) Pump; g) Vaporizer;
h) Product container; i) Cooler; k) Condenser; l) Vacuum pump; m) Container for condensed vapors
bulk densities of 5 – 70 kg/m3 . More than 60 %
of the foam is in the form of open cells.
Whereas UF foams previously could be
prepared only in factories of fixed location,
W. Bauer in 1953 described a transportable ap-
paratus that permitted on-site production of the
foam by means of compressed air [55]. A num-
ber of other apparatuses subsequently were de-
veloped. The state of the art is reported in [56]
with respect to the design of foam-producing ap-
paratus and a novel high-performance apparatus
of this type is described. The development of
foam-producing apparatuses led to much wider
applications: soil conditioning in agriculture,
heat insulation, sound insulation, filling of min-
ing cavities, carrier material for cleaning fluids,
and covering for landfills.
6. Environmental Protection
All necessary measures possible, according to
the state of the particular art, must be taken
during the production and processing of amino
resins to avoid air and water pollution. Regula-
tions constantly become more stringent.
Regulations or recommendations concerning
concentration of formaldehyde in rooms are:
Denmark 0.15 mg/m3
Finland 0.15 mg/m3
Italy 0.12 mg/m3
Netherland 0.12 mg/m3
Sweden 0.48 mg/m3
Switzerland 0.24 mg/m3
Germany 0.10 mg/m3
Effluents [57]. The condensed vapors or ef-
fluents from amino resin production may not
be introduced into water without biologic treat-
ment. It should be further ensured that these ef-
fluents cannot penetrate into ground water.
Waste waters or partially hardened residues
inevitably result when machines and contain-
ers are cleaned. The amount of wash water or
solvent should be kept as small as possible. If
the waste water contains predominantly urea or
formaldehyde, it can be reused in the production
process. Otherwise, it is eliminated, for example,
by incineration.
The biologic treatment of industrial effluents
from amino resin production is carried out pri-

marily because of the formaldehyde, which is
toxic. The usual effluents contain formaldehyde
in concentrations that can be degraded readily by
bacteria, which are always present. In general,
a critical factor in the biologic treatment of any
effluent is the concentration in which the various
toxic components are present.
Air. The treatment of waste gas by wash-
ing with water, catalytic combustion, or thermal
combustion is used in industry. The waste gases
should be very concentrated to minimize treat-
ment costs.
Solid Wastes. Amino resins can be solidified
by hardening them with ammonium chloride or
phosphoric acid, or they can be absorbed in saw-
dust or sand. In this form, they may be deposited
in a landfill in accordance with the relevant pro-
visos and legal requirements.
7. Types of Resins and Their
Properties
In addition to the simple types of
resin that are produced in the largest
amounts, i.e., the urea – formaldehyde and
melamine – formaldehyde resins, other types
of resin with different properties have been
developed. These are modifications, i.e., ver-
sions of a resin obtained by use of relatively
small amounts of additive or by changing the
aldehyde or amino component. However, even
where the composition is fixed the resin type can
be varied by changing the reaction procedure.
This leads to different distributions of oligomers
or to different substitutions of the repeat units.
The distribution of hydroxymethyl groups is the
determining feature.
7.1. Urea Resins (UF Resins)
All the urea – formaldehyde condensates
[9011-05-6] containing the repeat unit 1 (see
Chap. 3), from monomolecular product to high
molecular weight ones, are useful substances.
In the past few years, a number of discoveries
have been made concerning the composition of
UF resins. Systematic investigations into the
Amino Resins 13
process of condensation and the structural com-
position had long been impossible because of the
lack of suitable analytical methods. Industrial
development took place largely on an empirical
basis. However, using a combination of ana-
lytical methods, e.g., 1 H NMR spectroscopy,
13
C NMR spectroscopy, C, H, N, O elemen-
tary analysis, determination of hydroxymethyl
groups, and determination of total formalde-
hyde, it is possible in principle to determine the
structural units and their concentrations [22].
However, the relationship between the technical
properties of the amino resins or the materials
produced from these resins and the distribution
of the structural units is still unclear in most
cases, so development is still largely empirical.
7.1.1. Pure Urea – Formaldehyde Resins
Important macroscopic parameters are the molar
ratio of formaldehyde to urea, the viscosity, and
the gelling time. Urea – formaldehyde conden-
sates having a molar formaldehyde : urea ratio of
1 usually give insoluble polymethylene – ureas
that do not possess any adhesive properties. If,
however, the molar ratio is reduced from a rel-
atively high value gradually or stepwise in the
course of the reaction, the resultant resin pos-
sesses adhesive properties. These properties im-
prove as the molar ratio increases, but the un-
desirable release of formaldehyde increases si-
multaneously.
The highly viscous resin solutions obtainable
by prolonged industrial condensation of urea
and formaldehyde are low molecular mass prod-
ucts. They contain about six to eight urea units,
as can be determined by gel chromatographic
[21] and cryoscopic measurements and by end-
group determinations. This also applies to the
completely insoluble powdered or glassy con-
densates [58]. During storage, the concentra-
tion of methylene groups increases at the ex-
pense of the hydroxymethyl groups. The vis-
cosity also increases, initially slowly and vir-
tually linearly, and then, after a critical time,
rather steeply. Some or all of the hydroxymethyl
groups generally can be blocked by etherifica-
tion, and the shelf life of the amino resin is thus
extended [27], [59], [60]. In principle the same
reactions take place when the resin is hardened
by the user, but they are substantially more rapid.
14 Amino Resins
However, a residual amount of hydroxymethyl
groups remains after hardening [21]. Because
they are susceptible to hydrolysis, even the cured
urea resins are more water sensitive than the
melamine or phenol resins.
The gelling time [11, p. 174] or reactivity
of the resin is an important parameter for the
user. This time can be determined relatively pre-
cisely, and is the time in which the resin changes
from a fluid to a virtually immobile solid fol-
lowing the addition of a certain amount of hard-
ener at a particular temperature. The reactivity
increases with increasing molar ratio, content
of hydroxymethyl groups, and content of free
formaldehyde.
7.1.2. Mixed Condensates
Industrial amino resins contain mixtures of var-
ious condensates and cocondensates. Amino
resin solutions are always polymeric mixtures
having various degrees of condensation and dif-
fering distributions of functional groups. Resin-
forming monomers employed as textile auxil-
iaries constitute an exception, but these in them-
selves are not resins. The term mixed conden-
sates is rather loosely applied to those resins
which are formed in the condensation of urea
and formaldehyde when the reaction is car-
ried out using substances that also form resins
with formaldehyde. These are, for example,
melamine, phenol, organic acid amides, sulfon-
amides, and carbamates. Therefore, in the pres-
ence of melamine or phenol, it is possible to
prepare urea resins with improved strength and
swelling properties for the manufacture of parti-
cle board, i.e., weather-resistant particle board.
Modification with melamine gives resin glues
that can be used to produce good-quality parti-
cle board even when the molar ratio of formalde-
hyde to urea is low.
Mixed resins with other resin formers, e.g.,
acrylic acid, acrylates [61], [62], acrylamide [1,
pp. 109] and their derivatives, are also some-
times advantageous. These are also mixtures of
polymers, of cocondensates, or of homologous
polymers and cocondensates.
7.1.3. Condensation of Urea with Other
Aldehydes
Condensation of urea with isobutyraldehyde,
acetaldehyde, or crotonaldehyde is carried out
industrially to obtain sparingly soluble nitro-
gen fertilizers, i.e., controlled release fertilizers,
rather than resins [63], [64]. The condensation
of urea or melamine with glyoxal gives prod-
ucts that can be employed as textile auxiliaries.
Products obtained by the subsequent condensa-
tion of UF resins with glyoxal (e.g., DMDHEU
[1854-26-8]) also are used for textile finishing
[65], [66].
7.1.4. Resins from Urea Derivatives
Condensation with urea derivatives or substitu-
tion products are well known, but these reactions
are of industrial importance only for making tex-
tile and paper auxiliaries. Reactions with alde-
hydes can take place depending on the hydrogen
atoms still present at the nitrogen, but the ability
to undergo condensation decreases sharply with
the size and number of substituents.
The reaction of a symmetrically disubstituted
urea derivative, e.g., N,N  -dimethylurea or dihy-
droxymethylurea dimethyl ether, with formalde-
hyde in an acidic medium gives cyclic urea
derivatives of the urone type [67, p. 9]:
Dihydroxymethylurone dimethyl ether,
bis(methoxymethyl)urone [7388-44-5] is used
industrially to provide cellulose fabrics with a
wrinkle-resistant finish. It has middling reactiv-
ity and stability to hydrolysis [68, pp. 164 – 174].
The urones do react with cellulose but form only
minor amounts of self-cross-linked resins, such
as the urea – formaldehyde compounds.
When S is substituted for O in urea, thiourea
is obtained. The latter undergoes all of the
principal condensation reactions of urea. In
a weakly alkaline medium, N-hydroxymethyl
compounds and S-hydroxymethyl compounds
are formed. The tautomeric structure NH2 –
C(SH) = NH may be assumed initially for the

latter. The thiourea – formaldehyde condensates
are more water resistant than the corresponding
urea condensates. Some of the thiourea conden-
sates are assumed to be cyclic compounds [69].
7.1.5. Modified Urea Resins
There is very extensive literature on the possible
methods of modifying amino resins [1, pp. 95]
and only the most important modifications are
discussed here.
Reactions with Alcohols. The hy-
droxymethyl groups can be etherified with alco-
hols in an acidic medium [13, pp. 334].
The equilibrium constants for the etherifi-
cation of monohydroxymethylurea and dihy-
droxymethylurea with methanol and ethanol
have been measured [59]. The enthalpy of re-
action, estimated from the temperature depen-
dence of the equilibrium constant, is ∆H = − 6
to − 8 kJ/mol. The equilibrium constants (K)
differ depending on the substitution:
As the number of C atoms in the alco-
hol increases, the equilibrium is shifted and
the reaction rate reduced so that the etherifica-
tion becomes more difficult. The ethers of the
low-boiling alcohols can be transetherified with
higher boiling alcohols by heating the mixture
in weakly acidic solution and distilling the more
volatile alcohols [13, p. 336].
Frequently only some of the hydroxymethyl
groups of resin glues and impregnating resins
undergo etherification with monohydric or poly-
hydric alcohols of less than five carbon atoms.
As a result, some of the hydroxymethyl groups
are protected against condensation, and the
Amino Resins 15
resins have a longer shelf life [1, p. 115], [70],
[71]. In the starting materials for surface coat-
ings, 20 – 100 % of the hydroxymethyl groups
undergo etherification, depending on the type.
The amino resins etherified with butyl groups
are the most important for wood coatings, e.g.,
parquet coating. Where complete etherification
takes place, the reaction is carried out using an
entraining agent – the alcohol itself, toluene, or
xylene – and the water is distilled azeotropically.
Ethers of one- to three-carbon alcohols
with low molecular mass hydroxymethyl com-
pounds of urea, ethylene urea (imidazolidi-
none [28906-87-8]), propylene urea (1,3-bis(hy-
droxymethyl)tetrahydro-2-(1H)-pyrimidinone
[65405-39-2]), and melamine have achieved
some importance in the field of textile auxil-
iaries [3, p. 168], [59], [68]. These compounds
are precondensates having relatively low molec-
ular masses, about 600.
Urea resins etherified with butyl groups can
be employed as starting materials for mak-
ing surface coatings. However, when baked
alone, they give brittle and water-sensitive films.
Therefore they cannot be used alone as binders.
In combination with nitrocellulose, or with
alkyd, epoxy, or acrylate resins, they give ex-
cellent baked finishes.
Reactions with Ammonia and Amines.
Amines are very reactive toward hydroxymethyl
compounds obtained from urea and formalde-
hyde. Ammonia reacts with the hydroxymethyl
group to form an amino or imino group, elimi-
nating water:
-NH-CH2 OH + NH3 −→ -NH-CH2 NH2 + H2 O
The reaction of ammonia with formaldehyde
is exothermic (∆H = − 57 kJ/mol) [1, p. 49] and
gives hexamethylenetetramine. This reaction
has been used industrially to trap formaldehyde
16 Amino Resins
from waste gases, for example, from particle
board production [72–74]. The reaction of urea
and aldehydes with primary amines gives cyclic
compounds (triazines) [75] of the type 10, where
R can be hydroxymethyl and its methyl and
ethyl ethers.
Ammonia, primary or secondary amines, or
polyamines containing two or more primary
amino groups are used for the production of
amino-modified resins [3, p. 206]. They are
more stable to water than the unmodified resins
produced by a similar procedure.
As shown in the equation above, ammonia
and amines can react with the hydroxymethyl
groups in urea, in a weakly acidic or alka-
line medium, to give N-aminomethyl groups.
In strongly acidic solution, these eliminate the
amine substituents to form condensates. This
condensation is similar to that starting with
hydroxymethyl groups. Even very highly con-
densed urea resins are able to bind large amounts
of ammonia and amines because a substantial
part of the formaldehyde is still present in the
form of hydroxymethyl groups. This reaction is
utilized industrially, for example, to deodorize
resins or particle board [72].
Condensation of the resin molecule with an
amine produces a resin that has a cationic charac-
ter; this increases the resin’s affinity for cellulose
fibers when it is used as an auxiliary for textiles
or paper. These basic urea resins are therefore
mainly important because they improve the wet
tensile strength of paper.
Reaction with Sulfites. Just as formalde-
hyde hydrate reacts with a sulfite, so the hy-
droxymethyl groups of the amino resins react
with a hydrogen sulfite or a sulfite to give an
aminomethanesulfonate [1, p. 120]:
R-NH-CH2 OH + [HSO3 ]−
−→ [R-NH-CH2 SO3 ]− + H2 O
This imparts an anionic character to the resins
[3, p. 206]. The pH of the solution controls its
sulfite content.
[SO3 H]−
[SO3 ]2− + H+
To produce resins of this type, the reaction of,
e.g., urea and formaldehyde is begun in a neu-
tral or alkaline medium in order to achieve hy-
droxymethylation. When the desired degree of
conversion has been achieved, condensation is
carried out using sulfite or hydrogen sulfite in
a slightly acid solution [76]. However, the resin
can react with a hydrogen sulfite because many
hydroxymethyl groups are still present. Water-
insoluble resins can even be rendered soluble
by posttreatment with a hydrogen sulfite. Al-
though, like unmodified resins, the amino resins
produced using sulfites exhibit an increase in
viscosity on aging, they remain water soluble
because of their hydrophilic ionic groups.
The anionic resins are of particular industrial
importance in the field of water-soluble or water-
dispersible adhesives. Other uses include textile
auxiliaries [77], paper auxiliaries [78], leather
auxiliaries, and deodorants [79] for UF resins
[80].
In addition to modification with sulfite, the
relevant patents mention many other modifiers,
such as aldehydes and triazines. The affinity of
the anionic resins for cellulose (which carries a
slight negative charge) is lower than that of the
cationic resins; therefore, the fibers must be post-
treated with aluminum sulfate to fix the resins.
The modification of urea – formaldehyde
resin glues with ligninsulfonic acid should be
mentioned also [81], [82]. The products are dark
resin solutions that have been used from time to
time in the woodworking industry. The mecha-
nism involved in the incorporation of the nonuni-
form lignin is still unclear [1, p. 120]. Lignin
contains phenolic groups. Incorporation of the
lignin components imparts relatively high water
resistance, among other things. The lignins are
of different origins and compositions, so that the
production process must be adapted empirically
to the different lignin varieties. This fact and the
dark coloration have prevented more extensive
use of lignin wastes from wood pulp production.

7.2. Melamine Resins
7.2.1. Unmodified Melamine Resins
Melamine [9003-08-1], like urea, can react
with formaldehyde [9, p. 65]. The addition of
formaldehyde at the amino group is carried out at
pH 9 – 10 and takes place very rapidly. One mole
of melamine combines with 6 mol of formalde-
hyde to form hexahydroxymethylmelamine.
Melamine in itself is only slightly soluble even in
hot water [9, p. 60]. However, it dissolves read-
ily in aqueous formaldehyde solutions, form-
ing hydroxymethylmelamines. A small part of
the melamine remains physically dissolved.
When heated, hydroxymethylmelamines un-
dergo cross-linking [9, pp. 66] and form resins
that become more insoluble the longer they
are heated. Melamine condenses with formalde-
hyde in acid solution to form hydroxymethyl
compounds. This is followed by a more rapid
polycondensation, yielding cross-linked prod-
ucts, than in the case of urea – formaldehyde [13,
p. 359]. Melamine – formaldehyde resins can be
hardened thermally in the absence of a hardener
or they can be hardened in the absence of heat,
using a very strongly acidic hardener. The hard-
ening processes, as in the case of the urea resins,
are not entirely clear. Crosslinking takes place
principally via methylene bridges, but it also
has been suggested that methylene-ether bridges
play a role. The melamine formaldehyde con-
densates possess good thermal stability, optical
properties, and water resistance [13, p. 350].
7.2.2. Modified Melamine Resins
Reaction with Alcohols. Melamine hy-
droxymethyl compounds can be etherified
with alcohols in the same manner as hy-
droxymethylurea compounds [13, p. 361].
The most important use of the products
is as surface-coating resins, but they also
are used as textile auxiliaries and even as
melamine – urea – formaldehyde resins and im-
pregnating resins. As in the case of the urea
resins, etherification is carried out at relatively
high temperatures with acid catalysis. Where
etherification is carried out to a substantial de-
gree, it is important to remove the water or
excess alcohol from the weakly acidic solution,
Amino Resins 17
because cross-linking otherwise competes with
etherification. The mono- to hexaalkyl ethers
of the C1 to C4 alcohols can be prepared read-
ily. Good conversions are obtained for higher
alcohols only by means of transetherification
[83].
Methyl ethers of melamine hydroxymethyl
compounds are readily soluble in water even
at room temperature and crystallize readily [3,
p. 361]. The aqueous solutions of the methyl
ethers prepared from higher hydroxymethyl
compounds, i.e., those with a higher molar ra-
tio of hydroxymethyl groups, become cloudy on
heating and clarify again when cooled. Most
of the methyl ethers are soluble not only in
water but also in benzene and similar sol-
vents. The products etherified with higher al-
cohols, e.g., butanol or benzyl alcohol, are
water insoluble but are readily soluble in al-
cohols and some hydrocarbons. In addition
to monoalcohols, polyhydric alcohols, e.g.,
ethylene glycol, glycerol, 3-hydroxymethyl-1,5-
pentanediol, pentaerythritol, can be employed as
etherification agents. This etherification must be
carried out in neutral solution because the com-
peting cross-linking reaction otherwise takes
place more rapidly and forms insoluble prod-
ucts.
Like the corresponding urea resins, the
etherified melamine – formaldehyde resins used
as starting materials for surface coatings are
condensates having low molecular masses,
600 – 1400 [84]. These are presumably triazine
structures linked via methylene bridges and con-
tain from two to four melamine groups. The
ether groups are distributed randomly over the
triazine rings.
Reaction with Amines. Amines and
aminocarboxylic acids react readily
with the hydroxymethyl group of hy-
droxymethylmelamines in the same way as with
urea resins. Modification with amines or amino
acids improves the hydrophilic character of
the melamine resins. Condensation with amino
acids gives alkali-soluble melamine resins that
are used to produce impregnating or molding
materials [85]. Basic products, which form salts
with acids, are obtained by modification with
aminoalcohols, e.g., aminoethanol [86], and are
used as textile auxiliaries. These products are
not of major industrial importance.
18 Amino Resins
Reaction with Hydrogen Sulfite. Melamine
resins, like urea resins, react with hydrogen sul-
fites. Industrially, the cheapest product, i.e.,
sodium sulfite or sodium hydrogen sulfite, is
used, and the reaction is carried out in an acidic
or basic medium. The products are readily water-
soluble melamine resins that can be precip-
itated with acids. Hydrogen sulfite-modified
melamine – formaldehyde resins are used in-
dustrially as concrete liquefiers in the building
materials industry. In addition to sulfite, other
modifiers described in the patent literature are
dithionite and formaldehyde sodium sulfoxylate
(NaHSO2 · CH2 O) [87], [88].
Other Modifiers. The modification of hy-
droxymethylmelamine resins with polyalcohols,
sugars, toluenesulfonamides, lactams, nitriles
[89–91], acrylates, and polyacrylonitrile [1,
pp. 109], [92] is of great importance in the pro-
duction of impregnating resins. Such modifica-
tions improve the large number of laminating
properties required and stabilize the resin solu-
tion against clouding and excessively rapid in-
crease in viscosity.
Mixed condensates and cocondensates of
melamine with other compounds – e.g., phenol,
urea, cyanamide, and dicyanodiamide – that re-
act with formaldehyde have also been described
in a large number of publications. For example,
phenol-modified melamine – urea – formalde-
hyde resins are used as resin glues for weather-
resistant particle board [93], [94]. These resins,
too, can be modified in a large variety of ways.
7.3. Urethane Resins
Condensation of a urethane (carbamate) of the
formula H2 N–COOR with an aldehyde gives
a distinct compound or a resin, depending
on the production conditions [8, p. 220], [13,
p. 371]. In an alkaline medium, carbamates react
with formaldehyde to give hydroxymethyl com-
pounds that split up into the starting materials at
higher temperatures. In an acidic medium, they
cross-link to form methylene bridges and pro-
duce resins that are used to manufacture mold-
ing materials. A patent has been applied for re-
garding the use of urethane resins derived from
long-chain aliphatic alcohols as plasticizers [3,
p. 220]. Urethane – urea – formaldehyde mixed
resins have been described also. The reaction
of cyanuric acid with polyhydric alcohols and
formaldehyde gives resins that can be used as
paper and textile auxiliaries and as starting ma-
terials for surface coatings.
In another procedure, urea is converted to the
appropriate carbamate by heating in the pres-
ence of an alcohol and eliminating ammonia.
The subsequent reaction with formaldehyde and
cross-linking are carried out as described above
[13, p. 374]. The resultant highly viscous solu-
tions can be used as label adhesives and for the
adhesive bonding of cardboard boxes.
The properties of urethane resins vary de-
pending on the components and method of pro-
duction. They range from oily to brittle de-
pending on the degree of condensation. Lower
aliphatic and cycloaliphatic alcohols yield hard
resins, whereas higher alcohols give waxlike
resins.
7.4. Cyanamide and Dicyanodiamide
Resins
Cyanamide and dicyanodiamide react with
formaldehyde both in acid and in alka-
line media [8, p. 199]. Cyanamide reacts
with an equimolar amount of formaldehyde
at pH 6 – 7 to give a white precipitate,
which loses water to form a crystalline com-
pound. In general, cyanamide and dicyanodi-
amide are used as modifiers [1, pp. 118], [13,
pp. 382]. Cyanamide – formaldehyde and di-
cyanodiamide – formaldehyde resins have been
used as mixed resins for starting materials in
making molding compositions, as dyeing and
tanning auxiliaries, for textile finishing, and for
preserving urea – formaldehyde foams.
7.5. Sulfonamide Resins
The most commonly used basic component for
this type of resins is p-toluenesulfonamide:
With formaldehyde, p-toluenesulfonamide
forms resins that are fusible but not curable,
whereas disulfonamides or amides possessing

other groups capable of condensation give insol-
uble products that are infusible [95]. The special
properties of p-toluenesulfonamide resins in-
clude compatibility with cellulose surface coat-
ings, pale natural color (in contrast to that of
phenol resins), and low tendency to yellow.
Only the p-toluenesulfonamide – formalde-
hyde condensates have become important in-
dustrially, and these only as cocondensates or
modifiers. Only the combinations with urea –
melamine resins, phenol resins, and phthalate
resins are of importance [96]. They also are
added to melamine – formaldehyde impregnat-
ing resins as plasticizers in amounts of 3 – 8 %
[1, pp. 109].
7.6. Aniline Resins
Aniline resins include the condensates of
formaldehyde with aromatic amines, such
as aniline [25214-70-4], toluidines, xylidines,
naphthylamines, and phenylenediamines [13,
pp. 192].
In alkaline solution, the first stage, i.e., hy-
droxymethylation, leads to a simple condensate:
Condensation to give a cyclic product has
been reported also.
The reaction with formaldehyde in an acid
medium gives resins in which methylene groups
link the aromatic rings directly, as in the case of
the phenoplasts (→ Phenolic Resins). The para
position is activated by salt formation at the
amino group, so formaldehyde can add at this
position to form p-aminobenzyl alcohol.
Amino Resins 19
Polymer chains are formed and water is elim-
inated in this process. In the presence of an
excess of formaldehyde, three-dimensional net-
works also form.
The amino groups have a directing function,
so tertiary aromatic amines also can form resins.
Unlike the phenol resins, aniline resins do not
harden further. The aniline resins are therefore
thermoplasts in contrast to the resins discussed
above, which are duroplasts. The aniline resins
are not very important industrially. They have
been used in small amounts in the production of
molding materials [1, p. 120] and ion-exchange
resins and, because of their high resistance to
tracking currents, they have been mixed with
epoxy resins and used for wire enamels and in-
sulating coatings [97].
8. Analysis
Analysis, insofar as it is used for product control
during production, storage, and use, amounts to
testing various types of resins for characteristic
parameters or selected specifications. Complete
elucidation of the chemical structure, including
the sizes and amounts of the oligomers, would
entail an unacceptably great expense.
Characterization of the products usually
includes the following determinations [11,
pp. 171], [98–100]:
density in g/cm3 (in the case of foams, in
kg/m3 )
solids content in % by mass
viscosity in mPa · s, usually at 20 ◦ C
free formaldehyde
total formaldehyde
free urea
total urea
melamine
methoxy content
ash content (incombustible modifiers)
The urea – formaldehyde or amino groups –
formaldehyde molar ratio is calculated from the
analytical data.
Further tests may be employed if special
properties are required of the resins. The de-
velopment of novel products and applications
increases the need for analytical effort.
Solids Content. The determination of the solids
content in resin solutions is a determination of
20 Amino Resins
the dry matter content. The value is useful only
for comparison. It is determined by evaporating
the volatile components at 100 – 130 ◦ C over a
fixed period of time. This procedure removes not
only the water present as a solvent and the free
formaldehyde, but also the water and formalde-
hyde formed during the drying process in the
condensation. Therefore the dry matter content
is by no means to be equated with the active in-
gredient content. More exact data are obtained
by the determination of water by the Karl Fis-
cher method [101], by freeze drying, or, in or-
ganic solvents, by the Aufhauser method. In in-
dustry, however, the water content is estimated
by the drying method detailed above because
this method is simple and quick.
Formaldehyde [102–104]. The free formalde-
hyde can be determined directly and the total
formaldehyde can be determined after the prod-
uct has been hydrolyzed completely. The hy-
droxymethyl content can be determined by hy-
drolysis under relatively mild conditions. The
formaldehyde bonded in the form of methylene
groups is calculated by difference.
Urea. The total urea can be determined by hy-
drolysis and the Kjeldahl procedure. The free
urea is degraded to ammonia by the enzyme ure-
ase [105]. If no other form of nitrogen is present
in the resin, the urea content can be calculated
from the nitrogen content, which is determined
by combustion analysis.
Melamine in amino resins is determined by hy-
drolysis of the product under mild conditions
followed by titration with perchloric acid. Resins
having a low degree of condensation can be
titrated directly using a computerized automatic
apparatus.
The molar ratio of urea to formaldehyde can
be calculated from the total content of formalde-
hyde. This ratio provides information on the
formaldehyde elimination to be expected.
Methanol is generally present in the form
of methoxy groups bonded to hydroxymethyl
groups via an ether bond; it is determined by
the Zeisel’s procedure.
Other components are important, particularly
where the resins are used as paper or textile aux-
iliaries or as starting materials for making sur-
face coatings. Some of these are maleic acid, gly-
oxal, phenol, and amines and sulfites. The meth-
ods of determination are discussed in textbooks
on analysis or, for example, in specific articles.
These substances are not determined during rou-
tine product control.
For research and development purposes, pa-
per chromatography, thin-layer chromatogra-
phy [106], column chromatography [107], gel
permeation chromatography, 13 C NMR spec-
troscopy [22], [31], [36], 15 N NMR spec-
troscopy [119], 1 H NMR spectroscopy (using
dimethylsulfoxide as the solvent) [31], [108],
and infrared spectroscopy are used.
9. Storage and Shipment
Aqueous or alcoholic solutions of amino resins
are stored in steel tanks with or without inter-
nal epoxide coatings, in stainless steel tanks,
or in containers made of fiberglass-reinforced
polyester resin. Temperatures above 20 – 25 ◦ C
must be avoided because they bring on rapid
condensation, which increases the viscosity and
soon renders the resin unprocessible. Rotary
pumps or – in the case of highly viscous liquids –
positive-displacement pumps, e.g., gear pumps,
are employed.
Powdered amino resins are packaged in air-
tight, plastic-lined paper sacks that are sealed
against moisture. Certain types of paper bags can
withstand tropical climates. Under high pres-
sure, the materials may solidify. Spilled product
is taken to a waste dump.
Liquid resin loads of up to about 250 kg
are dispatched in small polyethylene barrels,
whereas greater loads, up to about 1 t, are dis-
patched in polyethylene containers encased in
sheet metal. Larger amounts are transported in
containers, railroad tank cars, tank trucks, or ma-
rine tankers. Amino resins must be disposed of
if they are damaged or become unstable during
transport in tanks.
The relevant regulations governing the dis-
posal of amino resins differ from country to
country and even within some countries. A com-
mon feature of all the regulations, however, is
that the resin must be hardened by the addition
of acid curing agents and must be delivered to
a licensed landfill. Where leakage occurs during
transport, it is advisable to absorb the resin solu-
tion with any appropriate agent that is available
(e.g., sand or sawdust) and then to deliver the
resulting material for incineration. In the Fed-
eral Republic of Germany, amino resins are not

included among substances regarded as endan-
gering water.
10. Uses
The properties of amino resins have been
adapted by industry to a very large number of
applications. New uses are being developed con-
stantly and any list is bound to be incomplete.
Uses include the following: adhesives; im-
pregnating resins; molding materials; starting
materials for making surface coatings; auxil-
iaries for paper, textiles, leather, and flotation;
strengtheners for building materials; concrete
liquefiers; binders for glass fibers and foundry
sand casting; fire lighters; emery papers; flame
retardant coatings; flameproofed combustible
items; foamed resins for many purposes; grind-
ing wheels; ion-exchange resins; sewage floccu-
lants; and microcapsule production.
The largest amount of amino resins is con-
sumed by the woodworking industry. These
resins, along with the phenol resins, have largely
replaced the natural glues based on proteins
(glutin, casein, soybean, and blood albumin
glues). Impregnating resins are used as resin
glues in the particle board, plywood, and fur-
niture industries. Impregnating resins also are
used to impregnate papers for decorative lami-
nates and for coating wood particle board.
Resin Glues for the Woodworking Indus-
try. The amino resins used as glues in the wood-
working industry are available commercially
predominantly in the form of 55 – 70 % aqueous
solutions or as solids, for example, powders. The
powder resins entail lower transport costs but are
more expensive because of the costs involved in
drying them and must be dissolved by the user.
Whereas the powder resins have shelf lives of 1
year or longer if stored correctly, the liquid prod-
ucts, depending on the type, have shelf lives of
only 2 – 6 months. During this period the viscos-
ity remains within limits that permit the resin
to be pumped with a conventional pump. The
amino resins are more or less stable intermedi-
ates; condensation is completed by the addition
of a curing agent and/or by heat treatment. A
curing agent, e.g., ammonium chloride, is virtu-
ally always required for the urea resins, whereas
Amino Resins 21
melamine resins can be cured at 120 ◦ C. Com-
pared to the melamine or phenol resin glues, the
particle board made from urea resin glue has
lower water resistance and is not resistant to boil-
ing. If these properties are required, melamine
resin glues or mixed condensates of formalde-
hyde, urea, melamine, and/or phenol are em-
ployed.
In addition to water resistance, the tendency
to release formaldehyde is very important. If a
low level of formaldehyde release is desired, the
formaldehyde content of the resin glue must be
correspondingly low. In some countries the glue
must receive the approval of the authorities.
Over the past few years, MDF (medium-
density fiberboard) resins have become increas-
ingly important. The MDF resins are pure or
melamine-modified urea – formaldehyde resins
that have a low viscosity, about 200 mPa · s.
Other modifiers may be used also. Medium-
density fiberboard is used in the production of
furniture with structured surfaces [1, pp. 179],
[109, pp. 266 – 275].
From an economic point of view, the urea
resins are the most important amino resin glues
because they are inexpensive and possess tech-
nical properties adequate for most purposes.
The main use is in the production of wood
particle board. These resins also play an im-
portant role as glues for plywood and block-
board and for furniture construction. The gluing
of load-bearing wood components and shutter
panels and the production of shaped articles are
further examples of the large variety of uses of
amino resin wood glues.
Impregnating Resins. Urea – formaldehyde
or melamine – formaldehyde impregnating
resins are used to treat papers for decorative pur-
poses. The resins themselves are brittle products
and it may be necessary to modify them with
a plasticizer. Because of their good properties,
i.e., hardness, abrasion resistance, scratch re-
sistance, and stability to light, the amino resins
are particularly suitable for this purpose. The
impregnated papers are used either to produce
decorative laminates or for coating wood parti-
cle board. Papers impregnated with melamine
resin are more heat stable than those impreg-
nated with urea resin [110].
The paper webs impregnated with the amino
resin are dried in a furnace at 70 – 200 ◦ C and
22 Amino Resins

are stored under air-conditioning until they are most important are papers that impart a decora-
used. tive pattern to the board which itself consists of
Table 1. Trade names of amino resins used as resin glues and im-
several layers of phenol resin-impregnated kraft
pregnating resins paper.
Supplier Urea Melamine
Ground films and decorative films are like-
resins resins wise amino resin-impregnated papers and are
used in the same way as wood veneers in the
Nobel Hoechst Chim. Nobelamine Nobelamine
France furniture industry. These films generally are pro-
Société Chimique des Pressamine Pressamine duced from urea resins and to a certain extent
Charbonnages S.A.
CdF-Chimie also from melamine – urea resin mixtures.
France
BP Chemicals Cellobond –
UK
Molding Materials. Molding materials con-
Montedison Xylocolla – sist of a filler, e.g., cellulose or sawdust, and a
Italy binder, which can be a urea resin or a melamine
Società Italiana Resine Sirit –
SIR resin. The molding materials obtained from
Italy melamine resins are superior to those obtained
Aika Aika-Uri –
Japan
from urea resins because of their better harden-
Dainippon Ink Plyamine – ing properties, higher mechanical strength, and
Japan greater resistance to tracking currents and mois-
Mitsui Toatsu Chemical Uramin –
Japan ture [3, pp. 68 – 100].
Nippon Carbide – Nika Resin The molding materials are employed for ob-
Japan
Nippon Chemical – Suntop
jects in daily use; e.g., white electrical plugs,
Japan switches, covers, telephone accessories, and but-
Nippon Kasei Suiso-Bond – tons are made from urea resin. Melamine resin
Japan
Shooei Chemical S-Resin – is used for camping, hospital, and canteen table-
Japan ware, and for junction boxes and insulating com
Sumitomo Bakelite Igeta –
Japan
ponents. Mixed resins that combine some of the
Dyno Industrier Dynomin Dynomin properties of the individual resins are also used.
Norway The most important trade names of amino
Ciba-Geigy Aerolite Melolam
Switzerland resins used as resin glues and impregnating
Amer. Cyanamid UFR Cymel resins are given in Table 1.
USA Urac Melurac
Borden Cascomite –
USA Raw Materials for Surface Coatings. Pure
Monsanto – Scripset
USA – Resimene
amino resins are not very useful as surface
Reichhold Floramine Diaron coatings. The majority of the commercially
USA available amino resins used as starting mate-
Rohm and Haas Uformite Uformite
USA rials for surface coatings are etherified with
BASF Kaurit Kauramin butanol or isobutanol and dissolved therein [3,
FRG
Cassella (Hoechst) – Madurit
pp. 124 – 148]. Special brands are also modified
FRG with methanol, ethanol, or propanols.
CSL, Chemische Werke SAR – Because the surface coatings obtained using
Saar Lothringen
FRG amino resins are too brittle, these resins cannot
Henkel – Pressal be used alone as binders. However, they are very
FRG
Resart – Resart
useful in combination with other binders. Urea
FRG resins and melamine resins are the most impor-
Südwestchemie Supraplast Supraplast tant cross-linking components for alkyd resins.
FRG
Physically drying finishes are obtained by
adding amino resins to nitrocellulose finishes.
The addition of these resins improves the hard-
Various types of amino resin-impregnated pa- ness, body, and stability to light. The principal
pers are required for decorative laminates. The field of use is in furniture finishing.
 Amino Resins 23
Table 2. Trade names of amino resins used as surface coating resins Acid-curable finishes are obtained by adding
Supplier Urea Melamine alkyd resins or saturated polyester resins. These
resins resins finishes can be hardened by adding an acid, e.g.,
Vianova Viamin Viamin
hydrochloric acid, p-toluenesulfonic acid, or a
Austria phosphoric acid derivative, at an elevated tem-
UCB – Synkamine perature. The resulting coatings are very hard
Belgium
Syntova Syntamine Syntamine and resistant to scratches, solvents, and the ef-
France fects of light [3, p. 130]. Urea resins are more
British Industrial Plastics – Beetle important than melamine resins, particularly in
(BIP Chemicals)
UK furniture finishing and parquet sealing.
British Resin Prod. Epok Epok Coatings that can be cross-linked by heat
UK
British Paints – Syntex treatment alone are obtained by combining
UK amino resins with alkyd resins, saturated
ICI Paralac –
UK
polyester resins, heat-curable acrylate resins, or
Resia – Resmelin epoxy resins. Because of their good mechani-
Italy cal properties, their gloss, and their resistance,
Società Italiana Resine Siramin Siramin
SIR these baked finishes are extremely important in
Italy industrial metal finishing, for example, for auto-
Hitachi Kasei Melan Melan
Japan
mobile bodywork, household appliances, metal
Mitsui Toatsu Uvan Uvan furniture, and containers [111, p. 177].
Chemical Because they are etherified and essentially
Japan
Sanwa Chemical – Nikalac free of water, the amino resins used in the
Japan surface-coating industry have shelf lives of from
Sumitomo Chemical Sumimal Sumimal
Japan
6 months to several years at room temperature.
Scado-Archer-Daniels Scadonur Scadomex They are dispatched in plain or galvanized sheet
Netherlands metal containers. Only stainless steel or alu-
Synres Nederland Synresin Synresin
Netherlands minum tanks are used for transport by tanker
Synthese Setamine Setamine trucks and railroad tank cars.
Netherlands
Dyno Industrier Dynomin U Dynomin M
The most important trade names of urea and
Norway melamine resins used as starting materials for
Perstorp Peramin – surface coatings are summarized in Table 2.
Norway
Svenska Olieslageri Soamin Soamin
Sweden Paper Auxiliaries. In the paper industry,
Ciba-Geigy Cibamin H Cibamin M amino resins are used to increase the dry tensile
Switzerland
Plüss Staufer – Plusamid strength and especially the wet tensile strength
Switzerland of the product [3, pp. 205 – 209], [112], [113].
Allied Chemicals Plaskon Plaskon
USA
In contrast to the procedure followed in the tex-
Amer. Cyanamid – Plaskon tile industry (see Textile Auxiliaries below), the
USA resin components are added to the paper stock
Monsanto – Resimene
USA before condensation. They are adsorbed onto the
Reichhold Plyamin Super fiber and then undergo condensation in an acid
USA Beckamine
Rohm and Haas Uformite Uformite
medium. The maximum strength of the paper
USA is reached only after a maturing period of 2 – 4
Texaco – Pantoxyl weeks. Based on the fiber, 1 – 5 wt% of resin
USA
BASF Plastopal Luwipal is sufficient to achieve good wet strength. The
FRG amino resins also are used for the surface finish-
Hendricks & Sommer Heso-amin Heso-amin
FRG
ing of papers. They impart water resistance to
Hoechst – Maprenal starch-containing paper-coating compositions.
FRG The urea resins, which constitute the most
Jäger Jägamin Jägamin
FRG important group, are generally hydroxymethyl
Stickstoffwerk Piesteritz Piadurol Meladurol compounds that have been modified by the ad-
FRG
dition of amines to give them a cationic character
24 Amino Resins

or by the addition of sulfites to provide an an- nantly monomeric, and therefore should not be
ionic character. After modification, these com- regarded as resins. They contain only unavoid-
pounds are subjected to a condensation reaction able, small, random amounts of higher conden-
in an acid medium. The resultant ionic resins are sates. The molecules react with the primary hy-
water soluble. The ionic character also enables droxyl groups of the cellulose on contact with the
them to be adsorbed onto anionic paper pulp, cellulose fibers. The relatively weak hydrogen
but anionic resins must be used with aluminum bridges of the cellulose molecules are thereby
sulfate [112, p. 43]. supplemented by additional, stronger covalent
Melamine resins also are important to the wet bonds. Self-condensation takes place on the sur-
strength of paper. In the absence of other modi- face of synthetic fibers, which do not react with
fiers, they react with acids to form strongly acid the “amino resin” monomers. This type of aux-
cationic colloids that are stabilized by an elec- iliary is discussed here, as are others that stiffen
tric charge and consist of partially condensed hy- the finish of synthetic fabrics.
droxymethyl melamines. Melamine resins mod- The pure urea – formaldehyde adducts,
ified with aminocaproic acid are also suitable mono- and dihydroxymethylurea, are water sol-
substitutes, either alone or in combination with uble and crystallize readily. In crystalline form,
other polymers, for some or all of the colophony they possess the largest share of the market for
soaps used in the internal sizing of paper [112, easy-care and wrinkle-resistant finishes for cel-
p. 42]. lulose textiles and mixtures of cellulose fibers
A further field of use is the production of with synthetics and wool. The pastes also consist
moisture-resistant starch pastes for the adhesive principally of these basic substances, but some
bonding of corrugated board [114]. of them are etherified with lower alcohols and
Trade names for aminoplasts used as paper exhibit a minor amount of condensation. They
auxiliaries are summarized in Table 3. are therefore used to provide wrinkle-resistant
and wash-and-wear finishes as well as stiff-
Table 3. Amino resins used as paper auxiliaries ened finishes on synthetic fabrics. The fabrics
treated in this manner possess improved wash
Supplier Resin
resistance. Hydroxymethyl compounds of urea
Rousselot Resin that exhibit a high degree of condensation and
France possess a high concentration of ether groups
British Industrial Plastics Beetle Resin
(BIP Chemicals) are used to produce highly elastic stiffening
UK effects and good wash resistance in cellulose
Mitsui Toatsu Chemical Uramin
Japan
fabrics. Because of the relatively low concen-
Sumitomo Chemical Sumires Resin tration of “amino resin” monomers (about 1 mol
Japan of resin per kg of cellulose), cross-linking be-
AKZO Etadurin
Netherlands tween the cellulose groups is strongly favored
Chemanord Casco-Resin over self-cross-linking. A disadvantage of this
Norway
Amer. Cyanamid Parez class of products is the relatively low stability
USA Paramel Regular of the acid treatment liquors in the bath, where
Resin condensation can take place easily between the
Hercules Powder Kymene
USA hydroxymethylurea molecules.
Monsanto Scriptite An important group is constituted by hy-
USA Resloom
Rohm and Haas Uformite droxymethyl compounds of cyclic urea deriva-
USA tives; examples are dihydroxymethylethylene
BASF Urecoll urea (11), dihydroxymethylpropylene urea (12),
FRG
Hoechst Madurit and dihydroxymethylurone (13).
FRG Acyclic compounds, such as various alkyl
carbamates, are also typical finishing agents. In
contrast to the pure urea – formaldehyde com-
Textile Auxiliaries. The textile auxiliaries pounds, these exhibit little tendency to form self-
based on derivatives of urea, melamine, and cross-linked resins and react predominantly with
formaldehyde [3, pp. 166 – 181] are predomi-
 Amino Resins 25

ferred for embossed finishes (Everglaze) where

the fabric can be damaged mechanically.
The most important trade names of the tex-
tile auxiliaries based on amino resins are sum-
marized in Table 4.

Table 5. Trade names of amino resins used as leather auxiliaries

Supplier Resin

cellulose to cross-link the fibers. The other ad- Hodgson Neosyn

vantages, over and above the mechanical prop- UK
BASF Relugan
erties, are resistance to chlorinated water, light- FRG
fastness, and shade constancy. These are closely Bayer Retingan
FRG
related to the chemical structure and the resis- Henkel Drasil
tance of the C–N and N–O bonds to hydrolysis. FRG
Chemtan Chemtan
USA

Table 4. Amino resins used as textile auxiliaries

Supplier Resin
Leather Auxiliaries. Resin retannage of
PCUK Diamonine chrome-tanned leather is carried out using
France
Dai Nippon Ink and Chemicals Beckamin hydroxymethyl compounds of urea, thiourea,
Japan melamine, dicyanodiamide, and ethers of these
Mitsui Toatsu Chemical Uramin [3, p. 211], [80]. Aqueous solutions of the resins
Japan
Sumitomo Chemical Sumitex Resin should penetrate the hide before condensation
Japan begins. The acid condensation catalyst (pH
Sandoz Finish
Switzerland 3.9 – 4.5) should not reduce the period of ac-
Monsanto Resloom tivity of the tanning liquor or damage the hide.
USA
Sun Chemical Permafresh
As in the case of the paper auxiliaries, the resins
USA are rendered cationic using amines or anionic by
BASF Fixapret means of a bisulfite. The anionic resins based on
FRG Kaurit
Ciba-Geigy/Pfersee Knittex melamine or dicyanodiamide make leather very
FRG Lyofix strong and supple and leave the color unchanged.
Henkel Stabitex
FRG
The hydroxymethyl groups react with the active
Hoechst Arkofix groups of the collagen fiber, which has a high
FRG content of glycine, proline, and oxyproline.
Hoechst Cassurit
FRG The trade names of a few leather auxiliaries
Thor-Chemie Quecodur are given in Table 5.
FRG

Other Uses of Amino Resins. The number

of possible uses is increasing constantly. The
Hydroxymethyl melamine derivatives and
uses listed at the beginning of this section are
their ethers are of some importance for provid-
summarized with the appropriate references in
ing high-grade finishes, i.e., embossed finishes,
Table 6.
Schreiner finishes, chintz finishes, and plisse fin-
The importance of many uses, e.g., flame-
ishes, but they have largely been replaced by
proofing agents, has declined greatly. Some ap-
the reactant types. The finishes obtained using
plications, e.g., casting resins, have proved un-
hydroxymethylmelamines are more wash resis-
satisfactory in practice, whereas others are only
tant than those made with hydroxymethylureas.
at the development stage and their industrial suit-
Hydroxymethylmelamine compounds are pre-
ability cannot yet be assessed.
26 Amino Resins
Table 6. Uses for amino resins

Application Resin and use References

Binders for glass fiber webs Reinforcing glass fibers in webs by means of urea resins [9, pp. 201, 214]

Foams Soil conditioning, covering landfills, heat insulation, lining [115], [1, pp. 196], [3,
tunnels in mines (→ Foamed Plastics) p. 161]

Foundry sand binders Binders for sand-casting in the foundry industry; casting molds [3, pp. 122]
and cores; modification with furfuryl alcohol

Concrete liquefiers and auxiliaries Sulfite-modified melamine resins [87], [88]

for building materials

Flame-proofing agents Flame-proofing wood by means of amino resins containing [1, p. 206], [3, p. 215]
phosphorus, boron, bromine, etc.

Ion-exchange resins Melamine-formaldehyde condensates modified with amines [3, p. 225]

Used for recovering silver from photographic effluents

Coatings for abrasive papers Urea – formaldehyde – furfuryl alcohol condensates for [3, p. 226]
imparting water-resistance

Wood preservatives Melamine – formaldehyde condensates impart good aging [3, p. 227]
resistance; no shrinkage; no seasoning cracks

Microcapsules Urea – formaldehyde resins [1, p. 289], [116]

Firelighters Emulsion of urea – formaldehyde resin with a liquid fuel and [117]
hardeners is processed to give small moldings. Lighting
oil-fired furnaces, charcoal grills, etc.

Sewage flocculants Urea – formaldehyde resins cause flocculation [118]

Table 7. Production of amino resins in the OECD countries

11. Economic Aspects
Year Production (106 tons)

1969 1.95
Amino resins have become increasingly im-
1970 2.03 portant since World War II. The OECD statis-
1971 2.20 tics “The chemical industry” and the production
1972 2.55
1973 3.13 statistics of the Federal Statistics Office of the
1974 2.79 Federal Republic of Germany refer the produc-
1975 2.47
1976 2.79
tion for the OECD countries shown in Table 7.
1977 2.94 The figures for Europe, USA and Japan are
1978 3.09 given in Table 8.
1979 3.33
1980 3.14 The production of particle board, which con-
1981 3.01 sumes the largest amount of amino resins in the
1982 2.69 Federal Republic of Germany, reached a high
1983 2.66
level by the late 1970s but diminished thereafter.
Comments: The figures for 1974 to 1976 and for 1979 exclude
Portugal. The figures include the phenol resins produced in the
Federal Republic of Germany. However, this qualification does
not greatly change the above figures for world production of
amino resins.

Table 8. Production of amino resins for Europe, USA and Japan

Production in 103 tons

1978 1979 1980 1981 1982 1983

Europe 1790 1890 1810 1690 1560 1420

USA 600 711 604 610 524 613
Japan 706 734 716 629 606 632

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Amino Resins 27
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28 Amino Resins
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