March 28, 1944- H. P.

-woHNslEDLER ET AL 2,345,543
CATIONIC MELAMINE-FORMALDEHYDE RESIN SOLUTIONS
Filed July s1. 1942

Z/?. ATTORNEY
 Patented Mar. 28, 1944
2,345,543

UNITED STATES] PATENT OFFICE

2,345,543
CATIONIC MELAMINE-FOBMALDEHYDE
RESIN SOLUTION
Henry P. Wohnsiedler, Darien, and Walter M.
Thomas, Stamford. Conn., assigner: to Ameri
can Cyanamid Comp
corporation of Maine any, New York. N.
Application .my 31, 1942, serai No. '453,120
3 Claims. (Cl. 26o-72)
This invention relates to compositions contain
ing aminotriazine-aldehyde condensation prod f, upon aging. ñrst to hydrophilic colloids, then to a
ucts, and more particularly to colloidally dis water-dispersible gel stage, and ilnally upon dry
persed aminotriazine-aldehyde resins having ing to a water-insoluble resin.
novel characteristics. (3) In the case of melamine-formaldehyde
Aminotriazine-aldehyde condensation prod condensation products the composition contains
ucts such as melamine-formaldehyde resins, am
meline-formaldehyde resins and resins prepared
by condensing formaldehyde with guanamines
have previously been prepared, both in the form 10 products of formoguanarníne, acetoguanamine,
of completely cured resins and in the form of wa ammeline and other amino-triazines.
ter-soluble or organic solvent-soluble intermedi (4) The pH of a 15% aqueous solution of acid
ates. The present invention relates, however, to type melamine-formaldehyde resin is always less
a new class of aqueous solutions of partially poly than 4.0 and is usually below 3.0. The ratio of
merized condensation products of these types in 15 acid to melamine in these resins varies with the
a colloidally dispersed condition wherein the con type of acid used being, in general, greater for
densation products possess new and hitherto un weaker acids than for stronger ones.
suspected properties. pH values and acid ratios '
We have discovered that aminotriazine-alde shown in Example 2'.
hyde condensation products, when prepared in We have discovered that aqueous solutions of
the presence of deñnite quantities of free acid or 20 the acid-type melamine-formaldehyde condensa
tion products will undergo a progressive poly
merization that is characterized by a gradual in
colloidal range is reached. `
25 We have discovered that the partially polymerized
melamine-formaldehyde resin carries a definite
portance, and particularly the property of mi
gration of the resin particles toward the cathode 80
upon electrophoresis of the dispersion. property in a solution of a heat-curable thermo
This invention is directed to colloidal disper setting resin, for it provides a ready method of
melamine-formaldehyde con obtaining a controlled deposition of the resin in
cationic aminotria
zine-aldehyde resin solutions are described and
claimed in certain copending applications that 35
will be identified hereinafter.
The colloidal solutions or dispersions oi' cation
ic aminotriazine-aldehyde resins may be pre
pared by the use of aminotriazines or aminotri 40 paper stock before it is formed into a ñnished
azine salts as starting materials, or they may be sheet, as is described inv detail in the copending
prepared from aminotriazine-aldehyde conden application of Chester G. Landes and Charles S.
sation products produced by conventional meth Maxwell, Serial No. 453,032, filed July 31, 1942.
The elapsed time necessary for aging a clear
solution of an acid-type melamine-formaldehyde
45 resin tothe colloidal condition in which it car
as “acid-type" resins or condensation products. ries a positive electric charge is dependent upon
The acid-type aminotriazine-aldehyde condensa the aging conditions. In general, the aging proc
tion products are readily identified by the follow
ing characteristics: ature or the concentration of the acid-typeresin
( 1) When freshly prepared they form clear so 50 solution, _'or by decreasing the amount of acid
lutions in both water and acids. present. The eiîects of variations
(2) The clear aqueous solutions are converted tors are shown in the following table, wherein
the resin under test was prepared as described in
42y 2,345,543
Example 1, paragraph ‘1, dissolved in boiling wa the aminotriazines, the melamine-formaldehyde
ter, vcooled and the correct amount o'i hydro resins constitute the preferred class of products
forv preparing the positively charged resin solu
chloric acid added. f „

' Resin; s ed at 1a’ F. A ed uw r.

Resin HC1 g g
00110., ratio
per œnt (mois) 24 hours - 48 hours 72 hours 24 hours 48 hours

1:1 Si. haze Gelicd.

i 1:1 Clear... _ Blue haze.

'I'he formation of a colloidal solution is shown i

tions of thepresent invention, since melamine is
relatively cheap and available in large quantities.
in the flrst instance by the presence of- a definite> Colloidal aqueous solutions of partially poly
Tyndall effect under the influence of a beam of
light or in the dark-field microscope. Although merized. positively charged melamine-formalde
the colloidal solution is inñnitely dilutable with -hyde resins having a glass electrode pH value
within the range of 0.5 to about 3.5 constitute a
water it is extremely acid-sensitive, and this con 20 representative but preferred class of the com
stitutes a very delicate test to determine whether `pounds of the present invention, and a typical
any colloidal acid-type resin is present. -. When a
Istrong acid such _as 6N hydrochloric acid is added solution of this type is illustrated on the accom
to a clear.~ acid-type resin solution that has not
panying drawing. In this drawing the positively
been aged no immediate change occurs, but when charged, colloidal melamine resin solution is
the acid-type resin has been aged for a time shown in the area marked “blue colloidal solu
sufficient to bring even a small part of the resin tions,” being bounded on both sides by the white
precipitates which form when not enough acid ,
particles within the colloidal range these parti or too much acid, respectively, is added. When
cles are precipitated by the addition of the acid. the proper quantities of acid are used the col
This reaction with strong acids can be used to 30 loidal range is preceded by the clear aqueous so
estimate the degree of polymerization of the resin .
lutions of acid-type melamine resin which are
solution since the amount of acid necessary for .
precipitation becomes less with increasing age of converted into the colloidal condition upon aging,
the solution. The colloidal range of polymeriza and is followed by gels which form when the ag
tion is easily apparent upon visual observationp 35 ing has been carried on for too long a time. It
for the originally clear solution of cationic mela will thus be seen that the positively charged,
mine-formaldehyde resin develops a character-` colloidal melamine-aldehyde solutions constitute
istic bluish haze when the colloidal solution has an intermediate stage between freshly prepared,
clear solutions and undispersible white or bluish
been formed. „
Although the above tests are useful methods 40 gels resulting from excessive aging, on the one
of identifying the colloidal solutions of partially » hand, andibetween white precipitates that form
polymerized melamine-formaldehyde resins of the by using too much or too little acid on the other
present invention, the most comprehensive test hand, and this is true of all the positively charged,
consists in the passage of a direct current through .
colloidal aminotriazine-aldehyde resin 4vsolutions
the solution. When the solutions of the present 45 oiiAny the present invention.
reactive melamine-formaldehyde resin can
invention are subjected to electrophoresis in this be prepared as or converted into a positively
manner the existence of a definite positive elec charged colloidal solution by following the condi
tric charge is shown by the migration of the tions outlined in the drawing. In every case,
colloidal resin toward the cathode, and this is an however, optimum amounts of acid within the
essential characteristic that is common to all the . 'range of about 0.5-3.5 moles per mole of mela
resin solutions of the present invention. The mine should be employed, and the resulting clear
cataphoresis is preferably carried out by pass solutions should be reacted by aging to a degree of
ing a direct current of 90-120 volts through plati polymerization less than that which character
num electrodes immersed in the colloidal solu izes the state of undispersible gel and precipitate
tion, a typical method of procedure being illus 55 formation, but suiiicient to bring the particles
trated in Example 3. thereof within the colloidal range. All the col
Aminotriazines containing one, two. or three loidal aqueous solutions of the present invention
reactive amino groups such as ammeline, amme are therefore characterized by having a glass elec
lide, formoguanamine, acetoguanamine, propiono trode pH value within the range of about 0.5 to
guanamine and N-substituted guanamines such about 3.5, a degree of polymerization suillcient to
as ‘iN-methyl- or «iN-ethyl-Z-acetoguanamines 60 bring the resin particles within the colloidal
may be reacted with formaldehyde or other suit range, and a deñnite positive electric charge as
able aldehydes to form a resin which may be used shown bythe migration oi the resin to the cathode
to prepare cationic, colloidally dispersed resin so upon electrophoresis of the solution. They are
lutions. However, these resins are noticlaimed also characterized by a content of about 2-2.5
as a part of the present invention, since they are 65
moles of formaldehyde for each mole of melamine
described and claimed in our copending applica and a .deiìnite blue haze in their colloidal solu
tions Serial Nos. 507,626 and 507,627, ñled Octo
tions.
ber 25, 1943. The invention will be illustrated in greater de
Water-soluble products prepared by heating the tail by the following speciñc examples. In the.
formaldehyde condensation products of melamine 70
or other aminotriazines with lower aliphatic al
interests of clarity the greater part-of the experi
in the presence of small ' mental data in these examples is presented with
cohols such as methanol _ reference to a relatively few specific compounds,
amounts of an acid catalyst may also be used. but it should be understood that similar results
Although cationic resin solutions can be prepared
from aldehyde condensation products of any oi' 75 are obtainable with all the acid-type aminotri
 2,845,548 /f
ezine-aldehyde resins and the invention in its 3
broader,y aspects is not limited by these examples. r tions are earned out in the presence of alcoholic
Example 1 ' r“
solutions, provided that at least 10% of water -is
present. With methyloi melamines and dry HCl
A methylol melamine having a ratio of form reaction in absolute alcohol leads to soluble prod
aldehyde to melamine of 333:1 was prepared by ucts which, however, do not have the characteris
heating together three melamine with 10 tics of the aqueous reaction products and will not
form colloidal, positively charged resin solutions
upon aging.
drying the resulting crystals. ` Example 2 ‘
Hexamethylol melamine was prepared by heat In the production of positively charged mela
1 mole of melamine and 8 moles of neutral 32% mine-formaldehyde condensation products which
aqueous formaldehyde solution on a boiling water will migrate to the cathode upon electrophoresis
bath until a clear solution was obtained, and then the molar ratio of acid to melamine is critical and
for‘lO minutes longer. The product was allowed depends on the type of acid and the time and
yto crystaliize and after two days was filtered, 15 temperature of the condensation reaction. The "
washed with alcohol and dried 5 hours at 60° C. effect of these variables is illustrated in the ac
15% solutions of these resins in water were pre companying dra , which shows the effect of
pared concentrated hydrochloric acid was added progressive additions of hydrochloric acid to a
in amounts such that the solutions contained 1 melamine resin solution at 15% solids. The resin
mole of HCl for each mole of combined melamine. 20 used was a melamine-formaldehyde resin con
The acidified solutions were then heated at 50° C. taining 3.3 moles of formaldehyde for each mole
for a total of 4 hours, during which samples were of melamine, prepared as described in the first
taken every 15 minutes during the first hour and paragraph of Example 1.
every hour thereafter and titrated for free (un Upon the addition of relatively small amounts
combined) formaldehyde. It was found that both 25 of hydrochloric acid to the solution a precipita
the resins liberated considerable quantities of free tion of a white amorphous resin occurs, and this
- formaldehyde during the first hour of heating and condition persists until a pHl of about 3.5 is ob
small quantities during the second hour, but no tained, corresponding to about 0.5 mole of HC1.
more formaldehyde was given olf during the last
two hours. After heating for two hours the 30 A transition zone is reached next, where cloudy
solutions setting to cloudy or opaque gel-like
amount of combined formaldehyde in the two resins are obtained, particularly upon long stand
resins was almost identical, and amounted to ap ing. With a slightly increased acid content, the
proximately 2.5 moles per mole of melamine. product is a clear solution which passes on aging
One mole of HC1 was then added to each of into a blue colloidal solution and then to a clear
two freshly prepared mixtures containing one bluish, water-dispersiblegel which can be redis
mole of melamine and 3 moles and 6 moles, re'~ persed to a positively charged, colloidal solution
spectively, of 32% aqueous formaldehyde solu by dilution with water and continued agitation.
tion, and these mixtures were heated for 4 hours However, these gels finally become undispersible
at 50° C. Determinations of the free (uncom on continued aging and set to clear insoluble res
bined) formaldehyde in the mixture containing 6 40
_moles of formaldehyde showed that only 2.5 moles ins on drying. Further increases in acid result in
were combined with the melamine after 2 hours the formation of clear solutions which Dass
heating, and no further amounts were combined through the stage of partial polymerization
after heating for an additional 2 hours. In the wherein the resin is positively charged, but final
other solution, which contained only 3 moles of 45 ly form white opaque gels after standing for sev
eral days. With a large excess of acid on the
formaldehyde for each mole of melamine, ap
proximately 2 moles of formaldehyde were com order of 3 or more moles of HC1 a two-phase
bined after the first two hours and very little more system is encountered (containing liquid together
entered into combination during the remainder with‘amorphous precipitate) which is quite sim
of the heating period. 50 ilar to those observed with insuilicient acid.
From the foregoing it is evident that the effect It vshould be understood that the molar ratios
of equimolecular amounts of hydrochloric acid on of acid shown in this chart will vary with the type
a melamine-formaldehyde resin is to produce a of acid. In general, larger quantities of weaker
ñnal product containing approximately 2-2.5 acids such as acetic and phosphoric acids are
moles of combined formaldehyde for each mole 55 necessary than with hydrochloric acid, but in all
of melamine. The foregoing experiment has been cases the DH range wherein the positively
repeated with phosphoric acid, acetic` acid, sul charged colloidal solutions are obtained lies be
furous acid and other water-soluble acids replac tween about 0.5 and about 3.5. The optimum pH
ing the hydrochloric acid in amounts sufficient values and acid ratios for typical acids is shown
to produce a pH of about 0.5 to about 3.5 in the in the following table.
solution, and in all cases the results are substan
tially the same as those described above. It is Acid Molesmoailiid
e O
evident, therefore, that formaldehyde in excess. ¿gamine goli tionî
of about 2-2.5 moles is liberated from methylol
melamines by the addition of these quantities of 65 HC! ..................................... _- 0. 7-1. I l. 5
acids, and that no more than this quantity of H00 0H l. 6-2. 6 3
vformaldehyde can be made to combine in their CHICOOH.
HIPO‘ .................................. _.
>2-31
)H
31. 5
presence. H18 0| .................................... _. 0. 5-1 3
When less than 2 moles of formaldehyde are
reacted with 1 mole of melamine in the presence Example 3
of' enough acid to produce a pH of about 0.5 to
about 3.5, pastes and solutions of only transient Representative Ímelamine-formaldehyde resin
stability are obtained rather than gels or clear solutions were prepared by the following pro
resins. Results identical with those obtained in cedure's: ‘ '

water solution are also obtained when the reac- _75 Resin 1.--A mixture oi' 126 parts by weight of
melamine (1 mole), 330 parts of 30% formalde
4 3,345,543 - s ‘ .

`hydef(3.3 moles) and 36.5 parts of _HC1 (1 mole) InCeHvery case where an acldined and aged resin
in the form of concentrated hydrochloric acid, solution was used the colloidal resin migrated
having an initial pH of 0.4, were reacted for 30 towards the cathode and therefore1 had a positive
minutes at 25° C., diluted with water to 10% electrical charge. The solution of Resin #4,
solids, and aged 5 days at room temperature. which was not aciditled and had a pH of 8,75
Resin 2.-1 mole of melamine. 3 moles oi‘ 32% actually migrated to the anode as shown by ni
aqueous formaldehyde solution and 1 mole oi’ HCl trogen analysis. _ .

were heated at 100° C. for one hour, then aged What we claim is:
24 hours at room temperature. - 1. A colloidal aqueous solution oi a partially
Resin 3.--5 grams of the resin described in Ex polymerized, positively charged melamine-form
ample 1, iirst paragraph, were dissolved in 20 cc. aldehyde condensation product having a glass
of water and 1.8 cc. of concentrated hydrochloric electrode pH value within the range oi' about 0.5
acid were added to give a pH of 1.6. The solu to about 3.5 when measured at 15 percent solids,
tion was then aged at room temperature for Z@ said condensation product containing about 2-‘2.5
_ hours. 15 moles of combined formaldehyde for each mole
Resin 4.-This was a non-acid type resin solu of melamine and having a degree of polymeriza
tion, prepared by heating a mixture of 1 mole oi' tion less than that which characterizes gels and
melamine and 3 moles of 37% aqueous formalde precipitates which are undespersible by agitation
hyde neutralized with NaOH to a pH of 7.2 for with water but sumcient to bring the particles
30 minutes at 60° C. after whichV the pHI was thereof within the colloidal range, said condensa
raised to 9.5. This solution had approximately tion product having a deñnite positive electrical
59% solids. charge as shown by its migration toward the
These resin solutions were subjected to electro cathode upon electrophoresis of the solution.
phoresis between platinum electrodes. A prelim 2. A colloidal aqueous solution of a partially
inary experiment on Resin #l was first made in polymerized, positively charged melamine-form
an ordinary U-tube with an electrode inserted aldehyde condensation product containing about
into each arm, and gave positive results which 0.7 to 1.3 moles of hydrochloric acid for each
demonstrated that the bluehazé o! the colloidal mole of melamine, said Acondensation product
melamine-formaldehyde resin solutions did actu containing about 2--2.5 moles of combined form
ally move to the cathode; in fact, a sizable 30 aldehyde for each mole of melamine and having
amount of resin Was actually deposited upon the a degree oi polymerization less than that which
electrode itself. However, the presence of hy' characterizes gels and precipitates which are un-`
drochloric acid resulted in the liberation of chlo dispersible by agitation with water but suihcient '
rine on the anode and caused a fiocculation of to bring the‘particles thereof within the colloidal
resin from the solution. at' range, said condensation product having a den
A modified cell was therefore- constructed in nite positive electrical charge as shown by its mi
which the blue resin solution was covered with gration toward the cathode upon electrophoresis
a layer of clear distilled water to permit easy of the solution.
observation of the migration and also to prevent 3. A colloidal aqueous solution of a partially
the high rate of electrolysis caused by the elecl 40 polymerized, positively charged melamine-form
trolytes in the solution. A11 the above resin so aldehyde condensation product containing about
lutions were subjected to caf ‘.phoresis in this cell, 2 to 3 moles of phosphoric acid for each mole of
using platinum electrodes having an areaof ap melamine, said condensation product containing
proximately 1 square inch and 120 volts poten about 2--2.5 moles of combined formaldehyde for
tial. The amperage varied considerably due tov 45 each mole of melamine and having a degree of
the varying amounts of electrolytes contained polymerization -less than that which character
izes gels and precipitates which are undispersible
in The
the solution.
following table ' .shows
, the resultsg of these by agitation with water but sufilcient to bring
tests: f the particles thereof within the colloidal range,
50 said condensation product having a deñnite pos
Resin No. itive electrical charge as shown by its migration
toward the cathode upon electrophoresis of the
1 l 2 3 4 solution. .
HENRY P. WOHNSIEDLER.
Duration J WALTER. M. THOMAS.
hours-. 6 ______ -_ 23 _ _ _ . _ _ _ _ _ _ . _ _ . _ _ _ _ _ _. 17.

Migration Cathode. Catbode_ Cathode Cathode. Anode.

towards. .
Gel deposited.. Yes--__. Yes-._-. Yes--_.. Yea--_-. No.
pH of solution:
Start _. 1.1--_-.. 1.6 .... -_ 8.75.
End.. 1.1 .............. _- 8.75.