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UNITED ‘STATES ' PATENT OFFICE

2,388,143
HARDENABLE AMINOTBIAZINE-AHJEHYDE
BESINS ,

Raymond 8. Harris, Stamford, Conn. ass or to v

American Cyanamid Company, NewgYorlkf'llv.
a corporation of Maine .
Y... -

No Drawing. Application October 5, 1943,

‘Serial'No. 505,031 ,
I 4 Claims. (Cl. 260-72)
This invention relates to substantially stable .
compositions containing an aminotriazine-alde ?uoride, into, an aminotriazine-aldehyde resin.
hyde resin and a curing catalyst. The following examples in which the propor
Many diil‘lculties are encountered in the stor tions are in parts by weight are given by way of
age 01’ dry aminoplastic resins such as the amino illustration and not in limitation.
triazine-aldehyde resins. These resins are pack Example 1
aged in the dry form alone or in admixture with
others for use as molding compositions, adhesives,
in the preparation of coating compositions, im-,
Dry water-soluble melamine-formaldehydeParts
resin _ _ 100
10 Ammonium silico?uoride________________ __ 0.8
These substances are blended together to form
the potentially acidic nature a homogeneous, stable, dry adhesive. The adhe
oi’ such catalysts as those which have heretofore ‘ sive prepared according to this examplemay be
been used, the resin has'become partially poly mixed with water in a ratio of about 65 parts oi.’
merized. Another difficulty is that many .sub- - the latter to about 100 parts of the resin adhe
stances which set free acid upon the addition oi sive. Such adhesive mixtures have a working life
water to the dry resin containing the catalyst of 2 hours or more at about 70° F. and they hard
are so active that the resulting solutions gel or, en in about 12-24 hours after application to wood
I surfaces to be Joined.
become too viscous to useas a glue or for coating 20 '
or impregnating purposes in an extremely short Optionally the bonded materials may :be placed
time. Other substances which have been used do in a kiln or oven at about 140° F. for several hours
‘ not produce su?lcient acidity to cause the resin in order to obtain thoroughly cured products in
a short time. ‘
to cure thoroughly at low temperatures and in
some cases such catalysts do not cause the resin Plywood bonded with a resin mixture of the
to cure even after a considerable time at elevated type disclosed has an extremely high shear
temperatures. These substances are, 01’ course, strength not only when dry but after immersion
unsuitable for use-in cold-set adhesives. in water at room temperatures for 48 hours and
Up to the time» of my invention cold-setting even after immersion in boiling water for 3 hours.
adhesives composed of melamine-formaldehyde 30 Example 2
resins did not produce bonds having satisfactory
shear strength. _ . .
Trimethylol melamine _- -v 80
Parts

An object of the present invention is to pro Walnut shell ?our_______________________ __ 17

vide curing catalysts for aminotriazine-aldehyde Tricalcium phosphate ___________________ .. 2
resins which will cause the latter to cure rapidly 85 Ammonium silico?uoride ________________ __ 0.5
and particularly in aqueous solutions.
Another object 01' this invention is to provide This mixture is blended so that all oi’ the in
aminotriazine-aldehyde resin compositions, in gredients are amply mixed, thereby producing a
cluding a curing ca _yst, which compositions are resin having excellent properties similar to those
substantially stable upon storage at ordinary tem 40 mentioned
prepared
above in connection with the products
according to Example 1.
peratures for a considerable period 01' time, e. g.,
six months-one year. Ammonium bororluoride may be substituted for
Still another object of my invention is to pro the ammonium silico?uoride used in the above ex
vide a melamine-formaldehyde resin adhesive, in amples. Ammonium boro?uoride is somewhat
cluding a curing catalyst, which adhesive has a 45 1ess active than ammonium silico?uoride and, ac
su?lcientworking life to be used commercially. cordingly. it I is desirable for use in summer
‘ A iurther object of my invention is to provide months when ordinary temperatures are higher
a melamine-formaldehyde resin adhesive; includ than in other parts 01' the year.
ing a curing catalyst, which adhesive exhibits My curing catalysts may be bu?‘ere'd by the
_ high shear strength when applied to wooden sur. addition 01' other substances, such as sodium for.
iaces and which is resistant to. water. mate, sodium acetate, disodium phosphate, sodi
um sulphite, etc. .
These and other objects are attained by incor My curing catalysts may be utilized in con
porating a small proportion of an ammonium salt junction with any'polymerizable amlnotriazine
01 a complex inorganic acid containing ?uorine, -
aldehyde condensation product. They are par
o. g., ammonium silico?uoride, ammonium bore ticularly suited for use in coniunction with the
 - 2,388,148
2 of surfaces including cellulosic sheets used in the
water-soluble aminotriazine-aldehyde resins espe manufacture of paper-board.
cially for use as adhesives. The term “water-solu My adhesives have an additional advantage
ble aminotriazine-aldehyde resin" as used here over conventional adhesives in that they are ver
in is intended to include those resins which form . min-proof since the ammonium salts which I .
colloidal solutions or dispersions as well as true employ as catalysts have insecticidal and insect
solutions. Any aldehyde condensation product repellent properties. , -
of any aminotriazine may be employed. Among _v The so-called glue line pH of my adhesive is
the aminotriazines, the following examples are above the minimum of 2.5 set by government
mentioned: Melamine, monophenyl melamine, 10 speci?cations. On the other handthe glue line
diphenyl melamine, triphenyl melamine, amme pH is sufficiently low to insure thorough cure
formoguanamine, ‘
line, thioammeline, ammelide, of the resin adhesive. '
acetoguanarnine, lauroguanamine, stearoguana While my curing catalysts are particularly
mine, etc. Other suitable aminotriazines are adapted for use in adhesives and especially for
those mentioned in U. S. Pat. No. 2,197,357. use in cold-setting adhesives, nevertheless, they
Various mixtures of any of the aminotriazines may also be used as catalysts in other resin com
may be used. Furthermore, mixtures containing positions containing an aminotriazine-aldehyde
aminotriazines such as those obtained by the resin. For example, they may be used in mold
thermodecomposition of dicyandiamide alone or ing compositions comprising such resins, together
in the presence of solvents, diluents or other re with ?llers, as well as for use in laminating syrups
active materials, such as aniline, may be em 20
for the production of laminated paper or lami
ployed. Any aldehyde may be used in accord nated cloth sheets. My catalysts are advan
ance with my invention, including formaldehyde, tageously used without the application of high
polymers of formaldehyde, benzaldehyde, fur temperatures and pressures as in the production
fural, etc. Mixtures of aldehydes mayalso be of laminated materials, but they may also be
utilized, for example, mixtures of formaldehyde 25 used in the high pressure and high temperature
and furfural. operations if desirable. Excellent core molds are
In some instances, it may be desirable to modify easily obtained by the use of an aminotriazine
the aminotriazine-aldehyde resins with other sub aldehyde binder such as a melamine-formalde
stances which are reactive with aldehydes to hyde resin binder containing my catalysts.
form resins, e. g., any urea, including urea itself, 30 Another application for my catalysts is in wa
'thiourea, dicyandiamide, aniline, phenol, resor ter paints containing urea-formaldehyde resins.
cinol, the cresols, xylenols, etc. If this be done, These paints may have suitable ?llers, dyes, pig
the modifier should preferably form a minor pro ments and extenders incorporated therein. My,
portion of the resin and in any event, the amino catalysts are also useful in coating or impreg-Q
triazine should be present in an amount of at nating compositions for use in 'the treatment of
least 5% based upon the weight of the other textiles, paper, leather and other ?brous ma
substance capable of forming resinous condensa
terials. -
tion products with aldehydes. , In any of the aforementioned applications of
Suitable resins may be prepared in accordance my catalysts, about 0.1-5% of the catalyst is em
with the disclosure of U. SJ Pats Nos. 2,197,357 ployed based upon the resin content.
and 2,269,239, as well as in accordance with an Obviously any modi?cation and variations of
application of Paul C. Schroy, Serial No. 356,655, compositions and processes described herein may
?led Sept. 13, 1940. _ be made without departing from the spirit and
For dry products such as adhesives, the initial scope of the invention as de?ned in the appended
aqueous condensation products may be dried in 45
any desired manner by vacuum dehydration, by claims.
drum-drying, by tray-drying or by spray-drying. I claim:
' 1. A hardenable aminotriazine-aldehyde con
My adhesives should preferably contain at least densation product intimately mixed with a cut
‘70% of resin, about 0-20% of walnut shell flour, ing catalyst which is selected from the group
any portion or all of which may be replaced by 50
consisting of ammonium silicofluoride and am
. wood ?our if desired and about 0.1—5% of cur
ing catalyst such as ammonium silicofiuoride or monium boro?uoride.
2. A water-soluble condensation product of an
ammonium boro?uoride. I have found that the aminotriazine and an aldehyde intimately mixed
products having specially desirable properties are with ammonium silico?uoride as a curing cat
produced by the use of about 0.6% of ammoni alyst.
um silicofluoride. In order to obtain a free-?ow 3. A water-soluble condensation product of an
ing, non-caking adhesive it is desirable to incor aminotriazine and an aldehyde intimately mixed
porate about 1-4% of some anti-caking' agent with ammonium boro?uoride as a curing cat
such as tricalcium phosphate. Furthermore,
gums, starches, dispersing agents or wetting 60 alyst.
4. An adhesive including a- dry water-soluble
agents may be included in my adhesive composi melamine-formaldehyde resin containing about
tions if desirable. ‘ 0.1-5_% of ammonium silicofluoride as a curing
' My adhesive compositions are ‘suitable for use catalyst intimately mixed therewith.
in the manufacture of plywood and also for join RAYMOND R. HARRIS.
ing wooden surfaces generally. They may also 65
be used as adhesives for joining a wide variety