United States I Patent [19] [11] Patent Number: 4,458,062

Blasing et al. [45] Date of Patent: Jul. 3, 1984

[54] CONTINUOUSLY PRODUCED MELT [56] References Cited
REACI‘ED MELAMINE-FORMALDEHYDE
RESINS U.S. PATENT DOCUMENTS
3,394,093 7/1968 Salem ............................ .. 528/254 X
[75] Inventors: Elmer P. Blasing; Ronald J. Keeling, 4,039,493 8/1977 Schon et al. .. 528/254 X
4,081,426 3/1978 Michel et al. . .... .. 528/254
Jin-Young K. Roe, all ofCincinnati. 4,168,370 9/1979 Ogden et a]. ................. .. 528/254 X
Ohio
[73] Assignee: American Cyanamid Company, Primary Examiner-——Lucille M. Phynes
Stamford, Conn. Attorney, Agent. or Firm-Frank M. Van Riet

[21] App]. N0.: 466,172 [57] ABSTRACT

A method for producing a melamine-formaldehyde
[22] Filed: Feb. 14, 1983 resin by reacting crystalline melamine and solid formal
dehyde in a single pass reactor, the resin produced by
[51] Int. Cl.3 .. ... . . . . . . . . . . . . . . . . . . . . . .. C08G 12/32 said process and a reinforcing substrate coated with said
[52] US. Cl. .................................. .. 528/254; 156/285; melamine-formaldehyde resin, are disclosed.
528/230
[58] Field of Search .............................. .. 528/230, 254 4 Claims, No Drawings
 4,458,062
1 2
reaction in a continuous reactor or feeding each compo
CONTINUOUSLY PRODUCED MELT REACTED nent into the reactor individually. Thecrystalline mela
MELAMINE-FORMALDEHYDE RESINS mine and solid formaldehyde, when blended, form an
essentially 100% reactive composition. They may be
BACKGROUND OF THE INVENTION blended together in any suitable mannersuch as by the
Amino resins, e. g. melamine-formaldehyde resins use of a mixer or other device which insures the forma
have been known and used commercially for over half tion of a homogeneous distribution thereof. Examples of
a century. Melamine-formaldehyde resins have histori coreactants include triethanolamine, hydroxypropyl
cally been prepared in aqueous solution in a single stage, melamine, 1,4-butanediol etc.‘ and examples of modi?ers
batch reaction. Although a majority of the melamine include any thermoplastic material melting within the
formaldehyde resins now commercially available are above range of reaction temperatures, for example, low
produced using batch reactions, continuously produced molecular weight, low density polyethylene, low-melt
resin is known. The commercial production of continu ing polyamides, biscarbamates and the like. Other. useful
ously produced resin however, requires cascade feeding modi?ers include ?bers, pigments, abrasives, microbnb
through a series of stirred tank reactors or reaction on a bles, stabilizers, absorbers, dyes and the like.
rubber mill, both procedures requiring extended periods The reactive components in the form of the resultant
of time. homogeneous blend or individual charges are fed into a
SUMMARY OF THE INVENTION continuously stirred, single-pass reactor such as a sin
gle-screw extruder, a twin-screw extruder, a kneader
It has now been found that melamine-formaldehyde extruder, a series of Moyno pumps, a great extruder i.e.
resins can be produced continuously utilizing short any reactor that transports a reaction product of in
periods of reaction so as to result in energy and labor creasing viscosity, at temperatures substantially higher
savings. The resins are produced as 90—l00% solid ma than those used to produce resins via a batch reaction
terials in the substantial absence of water or any other and for residence times of only a fraction of the normal
solvent. The process of the present invention results in 25 batch systems. In accordance with the instant invention,
the production of melamine-formaldehyde resins which temperatures ranging from about 120° C. to about 180",
exhibit properties materially different than prior art preferably from about 125° C. to about 155° C. and
solution produced resins when coated on reinforcing reaction times of from about 30 seconds to about 5
substrates. The instant process is very rapidv as com minutes, preferably from about 2 minutesto about 3
pared to known batch procedures and results in resins minutes, are employed. Under these conditions, an addi
which can be cooled and ground into powder or coated
onto reinforcing substrates while still molten. Utilizing tionreaction between the melamine and the formalde
the aqueous batch procedures of the prior art, in order hyde is achieved with a minimum of any condensation
to achieve a powdered resin, the liquid resin produced reaction occurring. Depending upon the speci?c condi
must ?rst be subjected to a drying step such as spray tions employed, the reaction can be controlled so as to
drying. Furthermore, if the resin solution produced is recover a resin of any desired melt viscosity, a possibil
used to saturate paper sheets in the manner normally ity; not achievable using known solution technology.
followed for the production of laminated articles, en The novel resins resulting from the process of the
ergy must be employed to evaporate the solvent from present invention may be recovered from the reactor as
the sheet after impregnation. Additionally, coreactants 40 av liquid melt or, alternatively, as a solid. They are, as
and modi?ers cannot be added to resin solutions unless mentioned above, addition reaction resins and are solid
they are co-solvable in the solvent employed. at room temperature. Upon exiting from the reactor,
The instant process allows the incorporation into the they are of high solids and contain small amounts of
melamine-formaldehyde resin of the necessary or de ‘water ,i.e._2'8%, and usually some unreacted charge
sired co-reactants and modi?ers during the resin forma 45 materials. They are normally 95—l00% resin and in a
tion. Furthermore, the resins formed can be coated molten state. '
directly onto reinforcing substrates for ultimate lami Upon recovery from the exit end of the one-pass
nate production immediately upon recovery from the reactor, the melamine-formaldehyde resins can be
reactor as molten materials. cooled to room temperature in any manner and ground
to powdery form utilizing known granulating equip
DESCRIPTION OF THE INVENTION ment.
INCLUDING PREFERRED EMBODIMENTS Alternatively, the resins which exit the reactor can be
The present invention comprises a continuous spread, while molten, onto a substrate e.g. paper, such
method for the one-shot preparation of a melamine-for as kraft paper, a-cellulose containing paper etc., non
maldehyde resin comprising: 55 woven webs, cloth, glass and the like. The resultant
(a) charging crystalline melamine and solid formalde novel coated substrates can then be cooled and stored
hyde in the absence of solvent and at a ratio of form and/or used in any desired manner such as for the pro
aldehyde to melamine ranging from about 1:1 to ductionof low or high pressure laminates. In the case of
about 3:1, respectively, into a single pass continuous paper substrates, the resultant coated paper is not brittle
reactor at a temperature ranging from about 120° C. 60 and can be rolled, a'feature contrary to paper which is
to about 180° C. for from about 30 seconds to about 5 treated with aqueous solutions of melamine formalde
minutes and ‘ hyde resins produced via batch procedures and then
(b) recovering the resultant resin as a molten material. dried. While not wishing to be bound by any particular
This process enables the manufacture of melamine theory as to why such coated paper sheets are ?exible,
formaldehyde resins utilizing a continuous process and ity is believed that the high solids and low water content
65. of the resins produced by the instant process enables
substantially solvent-free media. The process comprises
either blending the reactants, and any coreactants or them to be coated onto the paper without destroying
other modi?ers, together and then subjecting them to the hydrogen bonding of the paper or causing cellulose
 4,458,062
3 4
swelling and resin penetration‘ which‘ usually accompa tion is then cast into %" thick slabs and formed into
nies solution impregnation thereof. 1 = bathroom sinktops.
The following examples are set forth for purposes of
illustration only and are not to be construed as limita EXAMPLE 6
tions on the present invention‘except as set forth in the The procedure of Example 3 is again followed except
appended claims. ‘All parts and percentages are by that a commercially available thermoplastic acrylic
weight unless otherwise speci?ed. ‘ i‘ resin is admixed with the ingredients before extrusion.
A moldable product is recovered.
EXAMPLE 1
Two moles of ?ake paraformaldehyde, one mole of EXAMPLE 7
melamine crystals and 0.05 mole of triethanolamine are The procedure of Example 4 is again followed except
blended together in a suitable ‘mixer to form a uniform that the hot continuous discharge is coated in a nip
mixture thereof. This mixture is then fed into a one-pass, between the raw a-cellulose containing paper and a
‘single screw extruder operating at a‘ 130° C. barrel tem texturizing release sheet. The resultant paper assembly
perature and a screw speed controlled to result in a 5 is used in the manufacture of a high pressure decorative
product residence time in the reactor of approximately laminate between a phenolic resin impregnated kraft
three minutes. The resultant resin is discharged from "the paper core assembly and a polished press plate. An
reactor and then cooled to a solid mass. It is then me excellent laminate is recovered.
chanically ground. The powdered resin is dissolved in EXAMPLE 8
an alcohol-water solution. The solution is then used ‘to
impregnate an a-cellulose' containing ?dec‘or sheet, The procedure of Example 7 is again followed except
which sheet is then dried and heat-and pressure consoli that the texturing release sheet is replaced by an endless
dated into a decorative laminate, using ‘conventional release belt. When the paper resulting from this coating
phenolic resin impregnated kraft sheets ‘as ' the'co're, is used as the decor sheet in the production of a low
which passes all NEMA speci?cations‘. 25 pressure laminate on particleboard, an excellent lami
nate results.
EXAMPLE 2" ' _ .
EXAMPLE 9
To a suitable blending apparatus are added and
‘blended 1.6 moles of solid paraformaldehyde, ~l.0‘mole ‘The procedure of Example 7 is again followed except
of crystalline melamine, 0.07 'mole' of"l,'4-butanediol, that the endless belt is replaced by an overlay sheet. The
0.04-mole of triethanolamine and 0.08‘rnole of hydroxyl' %resultant overlay-decor composite is then used as the
propylmelamine. The resultant blend is processed using top layer of a high pressure decorative laminate, the
a continuous, one-shot, one-pass, single screw reactor
overlay sheet comprising the topmost layer. A decora
operating at 150° C. and a residence time of 1% minutes. tive- laminate passing all NEMA standards is recovered.
The hot discharge is immediately coatedonto-ta-‘cel EXAMPLE 10
lulose containing decor paper: and solidi?ed by cooling "The procedure of Example 1 is again followed except
to room temperature. When the paper ‘sheet is employed that a twin-screw extruder is used. Substantially equiva
as a component in a high pressure decorative laminate lent results are observed.
assembly as in Example 1 and heat and pressure consoli
dated, an excellent decorative laminate‘ results. i“ EXAMPLE 1 l
EXAMPLE 3 The use of a kneader extruder in lieu of the extruder
of Example 1 results in the production of an excellent
The procedure of Example 2 is ‘again followed except resinous product.
that about 10% of the total ingredients‘added to the 45
mixing apparatus includes titanium dioxide powder. EXAMPLE 12
The blended materials are fed through'the extruder at The procedure of Example 7 is again followed except
130° C. with a residence time of two minutes an'd'the that the heat continuous discharge is coated in a nip
continuous discharge stream is then cooled.‘ Thev solidi between the raw a-cellulose containing paper and a
?ed product is broken into lumps and further ground to decor sheet. An excellent laminate is formed.
a ?ne white powder. The powder is then mixed 'with We claim:
puri?ed wood ?bers, air-laid onto a foraminousbelt and 1. A continuous method for the one-shot preparation
molded into a solid reinforced sheet. of a melamine-formaldehyde resin which comprises:
EXAMPLE 4 . charging crystalline melamine and solid formalde
55 hyde, in the absence of solvent, into a single pass
The procedure of Example 3 is again followed except reactor at a temperature ranging from about 120°
that the hot continuous discharge is immediately coated C. to about 180° C. for from about 30 seconds to
onto a sheet of 60 -cellulose containing paper‘and cooled. about 5 minutes and recovering the resultant resin
The resultant sheet is used as the decor sheet in a'lhigh as a molten liquid.
pressure laminate assembly as in Example l'and heat and 2. The method of claim 1 wherein the resultant liquid
pressure consolidated into an excellent white decorative resin is cooled and ground into a powder.
laminate. _ ' ' ' i '
3. The method of claim 1 wherein said melamine and
EXAMPLE 5 i
said formaldehyde are homogeneously admixed before
charging to said reactor.
‘ The procedure of Example 3 is again followed except 65 4. The melamine-formaldehyde resin produced by the
that glass microballoons are added to‘thé" mixer" and process of claim 1.
processed through the extruder. The'resultant composi " It It a x a: