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Patented Oct. 1, 1946 7
2,408,682 '
Charles Arthnr'l'ortcr, Nutley, N. J., assignorto
Resistoiiex Generation, Bellevllle, N. 1.; a cor
poration of New York
No Drawing. Application December 28, 1944
Serial No. 570.222
12 Claims.
. _.
(01. 154—139) '
This invention relates to the adhering of poly
vinyl alcohol compositions to other materials,
more particularly to ?brous materials.‘
ethylene diamine, diethylene triamine, triethyl
ene tetramine, and tetraethylene pentamine.
These materials are preferably used as aqueous 4
In the making of a wide variety of mechanical
goods from polyvinyl alcohol compositions, it. is
frequently necessary or desirable to laminate the
plastic composition with one or more layers of
?brous material, such as textile fabric or paper,
solutions in concentrations of from about 5% tov
15%. The best range of concentration appears
' to be between about 5% and- about ‘7%.
The textile or other ?brous material may bev
_ immersed in the“ solution until it is thoroughly
> or to incorporate in the material strengthening
wetted, removed and dried at room temperature
' members in the form of cords or threads. of nat 10 to the point where it is Just slightly 'damp and
ural or synthetic ?ber, or inserts of ?berboard
~ and the like.
then laminated with the polyvinyl alcohol com
position and bonded thereto in the usual way with
It is particularly desirable that there be a ?rm
heat and pressure. Wetting can be accelerated
bond and strong adhesion between the polyvinyl
by the use of wetting'agents and may be accom-'
alcohol composition and the ?brous reinforce 15 plished by brushing or spraying as well as by dip
ment, especially in those cases where the product
is subjected to ?exing.
ping. By not completely drying the layer of re
One of the di?lculties -. _ inforcement, ' moistening it slightly if it has
heretofore encountered has been insu?lcient ad
been completely. dried, the adhering toit of the '
hesion with the result that in use the plastic :
composition has separated from its reinforcing 20
adjacent layer of polyvinyl alcohol composition
during molding is facilitated.
. The present invention appears to improve and
facilitate the adhesion of polyvinyl alcohol com
Laminated sheets of reinforced polyvinyl al
cohol compositions may be made by placing al- _
positions to all types of ?brous material, includ
ternate layers of the plastic and ‘?brous rein
ingnatural ?bers ‘of animal or vegetable origin as -
forcement in a mold and subjecting them to heat. 25 well as synthetic ?bers such as rayon. The ?-.
and pressure. In order'to obtain the proper ad
brous materialmay be in the form of threads,
hesion of'the layers to one another, it has here
cords, textile ‘fabrics, paper, cardboard, ?ber
tofore been necessary to control the pressure and
board and the like manufactured products, or in
temperature within close limits, slight deviations
the formiof a natural product such as wood 'or
therein resulting in imperfect adhesion. An 30
other di?iculty has been breakage of the ‘reinforc
ing layersv such as textile fabric and paper during
molding, ’due apparently to high friction between
~ _
tion, all of the water-soluble products resulting
35 from the partial hydrolysis of polyvinyl esters
sure which causes a certain amount of ?ow of
the plastic relative: to the reinforcement.
_ which may be of di?erent degrees of polymeriza
the polyvinyl alcohol composition and the fabric -
layer during the application of the molding pres
The term polyvinyl alcohpl, as used herein, in-.
cludes, in addition to pure polyvinyl alcohol,
and water-soluble partial derivatives of polyvinyl
' alcohol however formed.
Polyvinyl alcohol is
usually made by the partial or complete hydrolysis
~ The objects of the present invention are gen
era'lly to improve the adhesion between ?brous
of polyvinyl acetate and the commercially avail
materials and polyvinyl alcohol compositions, to 40 able varieties vary in their degree of hydrolysis,
enable the securing of more perfect adhesion
as indicated by the percentage of ester saponi
through a wider range of pressures and temper
?ed or by a saponi?cation number,-as well as in
atures. to eliminate breakage of reinforcing lay
ers during molding, and to produce more perfect
45 vinyl alcohol, as herein de?ned.
The present invention resides in the discovery
.- that greatlv improved results are obtained if the
?brous material-is subjected, preliminary to the
bonding operation, to the action of a dilute aque
ous solution of a linear ethylene amine having the 50
their viscosities in solution. The invention has
been found to be applicable to all types of‘ poly
The following speci?c examples will illustrate
the invention and show the advantages to 'be de
rived therefrom:
Exlmrns 1
A six inch square of muslin was‘ soaked in a 7%
aqueous solution of tetraethylene pentamine for
about 1 minute and dried at room temperature
wherein n is a whole number of 4 or less. The
until it retained only a slight dampness. The
compounds comprised within this de?nition are 65 thus treated fabric was used as an inter-layer be-_
tween two milled sheets of
polyvinyl alcohol
Exlmrm 3
composition about 3,!" thick, produced by the
Sheets of about 1/32nd of an inch in thick
method disclosed in U. S. Patent No. 2,177,612
ness were milled from a mixture having the fol
from the following ingredients, the proportions
being expressed as parts by weight:
lowing composition, parts being by weight:
Polyvinyl alcohol (91-94% saponi?ed, me
dium viscosity) _______________________ __ 100
Polyvinyl alcohol (91-94% saponi?ed me
Glycerol _______________________________ __
dium viscosity) _______________________ __ 100
Glycerol ____________________ ________' ____ __
__________ __, ________________ __
Water ____ ______________________________ __
Formamide ______________ __- ____________ __
Water ____ __. ___________________________ __
A six inch square of kraft paper was soaked in a
7% aqueous solution of tetraethylene pentamine
The assembly of textile and milled sheets was
until thoroughly wetted. The paper was dried
placed in an open mold in a platen press, heated
at room temperature until it had only a damp feel
to 260° F. in four minutes, then subjected to a
to the touch. It was then placed between two
pressure of 250 lbs. per sq. in. and cooled imme
pieces of the above milled sheet and exposed to
diately while still under pressure.
heat and pressure in an open mold, as in Ex
The adhesion of the polyvinyl alcohol compo
ample 1. The adhesion between the paper and
sition to the textile was excellent and the textile
the polyvinyl alcohol composition was very good
was not damaged in any way. Carrying out the
and the paper was not ruptured; When the pro
above procedure in exactly the same way except
cedure was repeated in the same manner except‘
that the treatment of the fabric prior to lami
that the treatment of the paper with the above
natingv was omitted, very poor adhesion was ob
mentioned solution was omitted, the adhesion
tained. vIn repeating the latter procedure with
was very poor. An increase of temperature and'
an increase in the temperature and pressure in 25 pressure improved, the adhesion somewhat but
an attempt to improve the adhesion, the fabric
ruptured the paper in several places.
interlayer was ruptured in places during molding.
Moistening the ?brous sheet of fabric or paper
with water will somewhat improve the adhesion
between it and the polyvinyl alcohol composition
under molding conditions but this expedient is
not satisfactory as the presence of water tends to
produce blister formation during molding and, .
since it does not decrease the friction between
While treatment of the'surface to be adhered
to the polyvinyl alcohol composition with the
linear ethylene amines of the invention has been
found to improve the adhesion of such composi 35 the paper or fabric and the polyvinyl alcohol
composition, it does not eliminate the .tendency
tions made with any grade of polyvinyl alcohol,
it has been found to produce the best results‘
with compositions made from thosegrades of
polyvinyl alcohol which are soluble in cold water,
for example the grade which is 85-88% saponi
fled and has a high'viscoslty. To take advan
of the pressure to rupture the ?brous sheet. One
of the particular advantages of the ethylene
amlnes'described herein is their lubricating eifect
‘ during molding which entirely eliminates ruptur
tage of this discovery when molding articles
comprising other grades of polyvinyl alcohol,
ing of the reinforcement.
The best results have ‘been obtained from the
higher members of the series of ethylene amines
thin intermediate layers of compositions made
with the cold-water-soluble types of polyvinyl
described above, namely triethylene tetramine
, alcohol may be used.
and tetraethylene pentamine and their use is
therefore preferred although all of the com
pounds named have been found to be useful for
Milled sheets of the fol
lowing compositions were prepared, parts by
Composition A
the stated purposes, the differences being a mat- _
Polyvinyl alcohol (85-38% saponi?ed, high
viscosity) ____________________________ __
Glycerol _______________________________ __
Formamide ____________________________ a-
Water ________________________________ _'__
Composition B
ter of degree only.
Since the foregoing examples are merely illus
trative of the invention, it is‘ to be understood
that it may be practiced otherwise than as herein
speci?cally set forth and that the invention is
to be construed broadly within the purview of
What is claimed is:
l. The method of making a composite product
comprising polyvinyl alcohol composition and
Polyvinyl alcohol (at least 98.5% saponi?ed,
~medium viscosity) ____________________ __ 10o
Glycerol _______________________________ __
Formamlde __________ __' ________________ __
Water _________________________________ __
fibrous. material in adhering'relationship which
0 comprises the steps of treating the ?brous me.
terial with a linear ethylene amine having the
in which n is a whole number of 4 or less, and
65 thereafter applying the polyvinyl alcohol compo
sition to the thus treated ?brous material.
aqueous solution of triethylene tetramine and
2. The method of claim 1 wherein the linear
dried at room temperature until just slightly
ethylene amine is applied as an aqueous solution
moist. It was then placed between two layers
and the ?brous material is substantially dried be
of'mllled sheet (formed as in Example 1) of
Composition A and this sandwich was then placed 70 fore application of the polyvinyl alcohol composi
tion thereto.
between two layers of similar milled, sheet of
3. The method of claim 1 wherein the applica
Composition B. The whole was then molded in
tion of the polyvinyl alcohol composition to the
an open mold under the conditions described in
?brous material is made by means of heat and
Example 1. Adhesion to the textile was excellent
75 pressure.
and there was no damage to the textile.
A six inch square of muslin was soaked in a 5%
4. The method 01' making a, composite article
comprising ?brous material and polyvinyl alco
hol composition comprising the steps of treating
said material with a solution of triethylene tetra
mine, evaporating most of the solvent, associat
ing the thus treated fibrous material with poly
vinyl alcohol composition, and applying heat and
pressure to adhere said material and composition.
oi’ cold-water-soluble polyvinyl alcohol, and sub
jecting the composite to heat and pressure where
by the materials are caused to adhere together.
7. A composite product comprising a layer of
?brous material containing a linear ethylene
amine having the i'ormula
wherein n is a whole number of 4 or less, and
5. The method of making a composite article 10 a layer of polyvinyl alcohol composition, said
comprising ?brous material and polyvinyl alco
hol composition comprising the steps of treat
layers being adhered together.
8. A composite product comprising a layer of
?brous material containing triethylene tetra
ing said material with a. solution of tctraethylene
mine, and a layer‘ of polyvinyl alcohol composi
pentamine, evaporating most of the solvent, asso
.ciating the thus treated ?brous material with 15 tion, said layers being adhered together.
9. A composite product comprising a layer of
polyvinyl alcohol composition, and applying heat
?brous material containing tetraethylene pent
and pressure to adhere said material and compo
sition together.
amine, and a layer of polyvinyl alcohol composi
6. The method of forming a composite prod
uct comprising fibrous material and polyvinyl
tion, said layers :being'adhered together.
alcohol composition‘which comprises treating said
?brous material is textile fabric. ' ‘
material with an aqueous solution of a linear‘
ethylene amine corresponding to the formula I
the ?brous material is paper.
wherein n is a whole number of 4 or less, evapo
rating most 01’ the solvent, associating the thus
vtreated material while damp with a composition
10. A product according to claim 7 in which the
11. A product according to claim 'I in which
12. A product according to claim 7 in which
polyvinyl alcohol composition is of the cold
water-soluble type.
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