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Патент USA US3041307

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rates “Pater
Patented June 26, i 962
Resins of this type which have been used with particu—
lar advantage are those, in the production of which, the
above-named constituents are used in proportions within
Charles Di Battistn, 716 Wiliow Sn, Craniord, NJ.
No Drawing. Fiied Jan. i6, 195?, Scr. No. 7S7,i29
5 Claims. (Cl. 26il—5)
the following ranges, by weight: ’
Phthalic anhydride _______________________ .._ 34—38
Pentaerythritol (maximum) ________________ __ 18—19
Drying oil acid __________________________ __ 46-51
The present invention relates to novel and useful plas
tic compositions having extraordinary adhesive and co 10
The alkyd resins described above are known and readily
hesive properties and which retain their plastic nature
available items of commerce, usually as 50% mineral
and high cohesive and adhesive characteristics over pro
spirits solutions. They have heretofore been proposed
longed periods under a wide range of climatic conditions.
for use in air-drying automobile ?nishes, fastv baking
These compositions are of particular utility for the ?ll
enamels and the like, but to my knowledge have not here
ing of expansion joints between concrete slabs in road
tofore been used in accordance with the present inven
building and as a surface coating for waterproo?ng roads
and the like.
One such resin solution of the type described above,
which I have found especially adapted for use in accord
- ture into the horizontal crack between sections of con
ance with this invention, is that marketed by American
crete of highways and will set to a plastic consistency 20 Cyanamid Company under its proprietary trade name
For instance, they may be poured at normal tempera
upon standing and will bond to the concrete even with
out the use of a priming coat.
“Rezyl Resin 811-1" having the following speci?cations.
Or they may be used as
a plastic composition in calking guns or by troweling into
vertically-extending cracks, likewise without the neces
sity of using a priming coat, and will bond thereto and 25
set in position without sagging and without exterior sup—
porting means.
These compositions of my invention are produced by
stirring the materials together, advantageously, at am
bient temperature for a period of about 1/2 minute. More
advantageously, these materials are mixed at the point
of use and only shortly prior to their use, the time period
between mixing and use depending primarily upon the 35
Solids ______________________ __ 50%.
Solvent _______ .._:___________ _. Mineral spirits.
Color (Gardner 1933) ________ _. 5-9.
Viscosity at 25° C. ___________ _. Z-Z3.
Pounds per gallon ____________ _. 7.8.
mixing a rubber latex, or a mixture of rubber latices,
with an alkyd resin of the type hereinafter described and 30
desired working consistency.
Solid resin:
Phthalic anhydride _________________ _. 35-38%.
Acid number _____________________ __ 4-10,
Pentaerythritol (maximum) _________ __ 19%.
Oil acids ____________________ __'_____ ‘16-49%.
Type of oil _______________________ _- Linseed.
A further resin solution of this type which I have also
used with advantage is one marketed by American Cy:
anamid Company under its proprietary trade name “Rezyl
Where the mixture is to be poured into horizontal
cracks or the like, it should generally ‘housed within 10
Resin 435-1" having the followingspeci?cations.
to 15 minutes after mixing. Upon longer standing, the
mixture develops a plastic consistency (such as inhibits 40 Solution:
Solids ______________________ __ 50%.
ready pouring but permits its use in calking guns or by
troweling, for instance, for ?lling vertically-extending
Solvent _____________________ __ Mineral spirits.’
cracks or for waterproo?ng porous surfaces.
Color (Gardner 1933) ________ _. 5-9.
The mixture, after setting, retains its pliable nature,
with retained adhesive and cohesive characteristics, un 45
der temperatures extending well below 0° Fahrenheit and
even under such low temperature conditions retains a
surprising degree of elasticit .
When used in road building, as ‘a ?ller betWeen con
crete sections, automobiles and trucks may be passed 50
over the road in 24 hours after application or in even
a shorter time period Where sand or the like is sprinkled
over the joint to prevent adhesion to the vehicle tires.
Upon contraction of the concrete sections following
Viscosity at 25 ° C. ___________ _Pounds per gallon __l_________ __,.
Solid resin:
, .
Phthalic anhydride ______ __, _________ _. 34-37%.
Acid number a. ___________________ _..\ 6-12.
Pentaerythritol (maximum) _________ ..-, 18%. '
Oil acids _____ _____________________ __ 48-51%.
Type of oil ___,_ _____ _; ___________ _. Soybean.
In the foregoing speci?cations, the proportion of the
constituent designated “oil acids” will be understood to be
on the proportion of acidic material present in‘ the _
a period of expansion, the composition is drawn back 55 based
drying oil. .
into the crack leaving no ridges, such as experienced
As the latex constituent of my compositions, I may
with conventional joint ?llers. Further, the composition
with advantage use either a natural rubber latex or a
is highly resistant to organic solvents, such as motor oil,
synthetic rubber latex, such as a latex of polymeric chlo~
gasoline and the like, and is unaffected by rock salt and
ropreen or a latex of butadiene-styrene copolymers ,or
other chemicals used in snow removal.
‘ . 60
mixtures of such latices. ‘I have with particular advan
The alkyd resin constituent, used in accordance with my
tage used a stabilized natural rubber latex herein desig
present invention, will be de?ned herein as a medium oil,
nated latex A.
oxidizing, phthalic-pentaerythritol alkyd resin modi?ed
The latex herein designated latex A is essentially an
by the incorporation therein of about an equal propor
suspension containing 50—55% natural rubber
tion of a drying oil acid. More particularly these resins
stabilized ‘by adding thereto, for each 100 parts
are the reaction product of phthalic anhydride and penta
of rubber solid, 2—6 parts of casein, as a protective colloid,‘
erythritol modi?ed ‘by, the inclusion therein of an oil
and about 3/10 part of a conventionally ‘used phenolic mold
acid of the linseed or soybean type in proportions approxii- -
mately equal to the combined weights of the phth'alic'
anhydride and Pentaerythritol, say about 45-50% of the
total weight of the modi?ed resin.
inhibitor, for instance, of the type marketed by Dow
Chemical Company under its proprietary trade name
“Dowicide-D,” and consisting essentially'of sodium
2-chloro-4~phenylphenate.' This latex A also contained
the following antioxidants’, expressed in parts by weight
composition to' be most satisfactory:
per 100 parts of rubber: ‘
.Zinc oxide ________________________ _a____'_____ 2
Zinc di-butyl dithiocarbarnate _____ __'_ ___________ __
tions, I have ‘found a mixture of latices of the following
Latex A __________________ _'___' _____________ __ 80
Latex B
p7(p-Tolyl-sulfonylamido) dimethylamine _______ __ 1A
Latex C _
Di- and tristyrenated phenol _______ _a __________ __ ‘.1
However, excellent results have been obtained using a
The chloroprene polymer latex which I have used with
mixture of these latices in proportions ranging from 50
particular advantage, herein designatedlatex B, also con 10 parts to 100 parts of latex A' in place of the 80 parts given
tained approximately 50-55% rubber solids and, except 7
for the nature of the rubber, its composition was sub-'
stantially identical with latex A, including the same pre
in the above tabulation. Likewise, the proportions of latex
B and latex C may respectively be increased to 100 parts,
servatives, antioxidants and stabilizing agents in the
used, or may be varied ~witlu'n the range of 50-100 parts
previously indicated proportions.
i.e. equal proportions of the respective latices may be
15 per 80 parts of latex A.
The further natural rubber latex, herein designated
In the latex' mixture described above, I have, with ad
vantage, used a small proportion of glycerine ranging from
latex C, which I have used with advantage, is the conven
tional ammonia-stabilized natural rubber latex of com
merce, which contains about 35-40% rubber solids.
In lieu of the latices just described, or in conjunction
1 part to 10 parts, more advantageously, about 3 parts,
based on the foregoing tabulation.
As a guide in determining the optimum composition
therewith, one may use )3. lbutadiene-styrene latex pre- _
served ‘and stabilized as is'latex A.
It ‘will be understood that my invention is not restricted
to the use of the particular resin and latex constituents
just speci?cally described but contemplates the use of 25
other resin and latex constituents of the same general
Most advantageously, I have used a mixture of the
of the latex constituent, it may be pointed out that the
setting of the resultant composition tends to be retarded
by the latex A while either latex B or latex C tends to ‘
hasten the set. An vincrease in the proportion of latex B
tends to increase the adhesiveness of the resultant com
position and to render it more resistant to hydrocarbon
solvents. An increase in latex C tends to increase the
cohesiveness of the resultant composition and the glyc
erine tends to prolong the plastic life of the composition
three types of latices just described for the reasons here- .‘
inaifter stated. I also prefer to incorporate in the mixture
a minor proportion of glycerine, but the invention in its
and to render it more pliable under low temperature
broader aspect is not so restricted.
Thus by selecting one or more of the above-noted
I may also incorporate in my composition various ?llers
latices tending to produce the required results and ad
of ‘an inert nature such ‘as talc, calcium carbonate, carbon 2 justing the proportion thereof in accordance with the
black, iron oxide, fuller’s earth or the like, or. in lieu of 35 foregoing directions, compositions suitable to meet a wide
such ?ller, or in conjunction therewith, I may incorporate
variety of needs may be produced. 7
?nely ground rubber in the mixture. In lieu 'of the mate
'While separate, either with or without the addition of
rial just mentioned, or' in conjunction therewith, I may
' a ?ller as previously described, ‘the resin constituent and
also add ‘Portland cement or “Lumnite” cement, the
the latex constituent, respectively, are stable over long
latter being a calcium-almninate cement of commerce. 40 periods of time and have been observed to have a shelf
As previously noted, the setting of the composition is
life of at least 5 months. But upon mixing, the setting of
initiated upon mixing the resin constituent with the latex
the mixture is initiated and the rate at which the setting
constituent. Therefore, these materials should be kept
occurs can be regulated,’ as previously described, by the
separate until just prior to use. Where an'inert filler is
composition of the latex'constituent. ‘ Thus the pouring
used, it may be premixed either with the resin constituent 45 time, i.e. the period of time. over which the composition
or with the latex constituent of it may be premixed in part
remains readily pourablemay be varied at will, say from
' with the ‘latex constituent and in part with the‘ resin con
5 minutes to 30 minutes, or even more. However, by
stituent. Where Portland’ce'ment, or other material which
thus extending the pouring time, the time required for the
tendsrto harden underfabsorption of water is, used, the
composition to set-up to a plastic consistency is likewise
premixjng of such material with a latex constituent
should be avoided. Under such conditions, the Portland
Where the composition is to, be used in a calking gun
cement or the like is,iwith"advantage, premixed with the
or .for troweling, a plastic consistency is, of course, desired
1 and this consistency is obtained merely by permitting
The proportion of ?ller added is subject to considerable ' the mixture to stand for one-half hour orrlonger, depend
variation depending uponthe desired properties of the
' composition. I have, with particular ‘advantage, used inert
?ller in proportions ranging ‘from 5% to 25% by weight
of the ?nished composition. Where a filler such as Port
land cement or “Lumnite" cement is used, most advan
ing upon the selected composition of the latex constituent,
until the desired consistency has been reached.
When a ?ller, such as previously mentioned, is pre
mixed with the resin constituent in proportions ‘such as
to render the mixture too still for ready mixing with the
60 latex constituent, more mineraljspirits or the like may
of the cement isiwithin the range of 5 parts to 20 parts ‘ . be added to the resin-?ller mixture in amounts. sufficient
ta'geous results have been obtained where the proportion
‘per 100 parts of the resin constituent.
The proportion of latex constituent to resin constituent
,7 may likewise be varied somewhat but usually‘ should ap
proximate equal proportions by volume. V
As previously noted, the latex eonstituenbrnay con
sist of a single latex or a mixture of latices. I have found, .
to'r'ender it su?iciently ?uid for ready mixing.
In addition to use as, a crack ?ller, my plastic composi
tion has been found to be especially useful for waterproof
ing roads having a surface of pervious material. For
a this. purpose,;a thin layer of my composition, after it has
set to a thin plastic consistency, is evenly spread in a thin
layer, for instance ranging from %.2 to 1%; inch, over the
however, that the characteristic of my composition may,
\yvith advantage, be varied when’ desired by using a mixture 70 pervious surface of the road. Advantageously, the sur—
face of the composition‘is then covered by a thin layer
of the respective latices and varying the proportion thereof
of sand which is then pressed into the composition by light
toobtain the desired results. I may thereby vary ‘the
rolling. This treatment not only provides a waterproof
setting time and the adhesive and cohesive characteristics
surface for the road butit does not chip or crack due to
of the product to meet various speci?cations.
temperature changes and also decreases road re
For most purposes, and‘under general working condi 75
?ection and glare and materially lessens the skidding haz
ume within the range of 1:3 to 3:1, the latex being of the
By conventional tests, it has been shown that the com
positions of my present invention may be distorted by
following approximate composition by weight: (A) a
natural rubber latex and (B) a chloroprene polymer latex,
50% or more and are sufficiently elastic, even at zero
stabilized by having incorporated therein, per v100 parts
each containing about 5'0-55% rubber solids and each
degrees Fahrenheit, to return to their original con?gura
of rubber solid, about 2-6 parts of casein, as a protective
tion when the con?ning surfaces are again moved apart
colloid, about 1,40 part of phenolic mold inhibitor, and
to their original positions.
about 2 parts zinc oxide, about 1 part zinc dibutyl dithio
The invention will be further illustrated by the follow
‘1A part p-(p-tolyl-sulfonylamido) di~
ing speci?c examples of my new compositions and the 10 methylamineabout
and about 1 part di- and tristyrenated phen
method of preparing and using the same.
ol, as antioxidants, and (C) ammonia-stabilized natural
80 parts of latex A, 20 parts of latex B and 3 parts of
rubber latex containing about 3,5440% rubber solids.
latex C and 3 parts of glycerine, each by weight, are
2. The composition of claim 1 in which there has been
mixed together with stirring and the resultant mixture is
incorporated a minor proportion of glycerine within the
mixed with an equal volume of a 50% solution of the
range of 1-10 parts. a
resin previously identi?ed herein as “Rezyl Resin 811-1”
3. The composition of claim 1 in which the propor
by stirring for approximateliy 1/2 minute at ambient tem
tions of the respective latices comprising the latex mix
perature. This mixture is then allowed to stand for ap
ture are approximately ‘as follows, by weight:
proximately 10 minutes at-which time the mixture is
found to be of good pouring consistency and is readily 20 Latex A
applied as a crack ?ller between the concrete slabs of
Latex B __
highways by pouring into such cracks to a depth such that
Latex C
the surface of the ?ller is ?ush with the highway surface.
When this mixture is permitted to stand for a longer
4. The composition of claim 3 in which the proportions
period of time before use, say in excess of about 15 25 of the respective latices comprising the latex mixture are
minutes, its consistency increases and upon standing for
approximately as follows, by weight:
approximately 1/2 hour is of a consistency suitable for use
in calking guns or for troweling or may be applied as a
Latex A
Waterproof surface coating to highway or other surfaces
Latex B ____________________________________ __ 2O
as heretofore described.
Latex C
_ 80
As previously noted, the glycerine may be omitted
5. The composition of claim 3 in which the proportions
from the mixture and the proportion of resin constituent
of the respective latices comprising the latex mixture are
to latex constituent is subject to considerable variation
approximately as follows, by weight:
without loss of the essential properties of the composition.
For instance, depending upon the intended use of the re 35
Latex A
_____ 80
sultant product, the proportion of latex constituent to
resin constituent may be varied within the range of 1:3
to 3:1 without loss of the advantageous properties of my
Latex B _______________________________ __ 50-100
Latex C _
_ 50-100
I claim:
References Cited in the ?le of this patent
1. A composition of matter resulting from stirring to
gether a medium oil, oxidizing, phthalic-pentaerythritol
alkyd resin, modi?ed by the incorporation therein of
about an equal proportion of a drying oil acid, in solution
in mineral spirits, with rubber latex in proportion by vol— 45
Carothers et al. _______ __ Feb. 4,
Robertson et al. ______ __ May 24,
Hahn _______________ __ June 3,
Crouch _____________ __ May 26,
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