U.S. patent number 3,847,637 [Application Number 05/336,138] was granted by the patent office on 1974-11-12 for stable wax sizing composition and method of sizing cellulosic fiber products.
This patent grant is currently assigned to United States Gypsum Company. Invention is credited to Myron Michael Luszczak.
United States Patent |
3,847,637 |
Luszczak |
November 12, 1974 |
STABLE WAX SIZING COMPOSITION AND METHOD OF SIZING CELLULOSIC FIBER
PRODUCTS
Abstract
A stable aqueous wax emulsion sizing composition comprising a
continuous aqueous phase; a waxy material dispersed phase
containing up to about 45 percent by weight of wax; about 10-15
percent by weight based on the weight of the waxy material of clay;
and a small amount of sulfuric acid. The sizing composition may be
applied to a variety of cellulosic products of a fibrous nature to
render the finished product water-resistant or waterproof.
Inventors: |
Luszczak; Myron Michael
(Palatine, IL) |
Assignee: |
United States Gypsum Company
(Chicago, IL)
|
Family
ID: |
23314740 |
Appl.
No.: |
05/336,138 |
Filed: |
February 26, 1973 |
Current U.S.
Class: |
106/271; 162/172;
162/181.8; 106/272 |
Current CPC
Class: |
D21H
17/68 (20130101); D21H 17/60 (20130101); C08L
91/06 (20130101); D06M 11/55 (20130101); D06M
13/02 (20130101); D06M 11/79 (20130101) |
Current International
Class: |
D21H
17/00 (20060101); D06M 11/00 (20060101); D21H
17/68 (20060101); D06M 11/79 (20060101); D21H
17/60 (20060101); D06M 11/55 (20060101); D06M
13/00 (20060101); D06M 13/02 (20060101); C08L
91/06 (20060101); C08L 91/00 (20060101); C08h
009/06 () |
Field of
Search: |
;106/271,10 ;260/28.5R
;162/172,181D |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Liebman; Morris
Assistant Examiner: Michl; P. R.
Attorney, Agent or Firm: Kurlandsky, Esq.; Samuel Hadley,
Esq.; Stanton T. Roberts, Esq.; Kenneth E.
Claims
What is claimed is:
1. A stable, aqueous wax emulsion sizing composition consisting
essentially of:
a. a continuous aqueous phase;
b. a dispersed waxy material phase containing up to about 45
percent by weight, based on the weight of the composition, of scale
wax;
c. about 10- 15 percent by weight, based on the weight of the waxy
material, of clay; and
d. an amount of sulfuric acid effective to facilitate
emulsification of said wax.
2. A stable, aqueous wax emulsion as set forth in claim 1, wherein
the wax comprises a crude scale wax.
3. A stable, aqueous wax emulsion as set forth in claim 2 wherein
the crude scale wax contains about 0.1 to about 10 percent oil
content.
4. A stable, aqueous wax emulsion as set forth in claim 2 wherein
the crude scale wax contains more than about 2 percent oil
content.
5. A stable, aqueous wax emulsion as set forth in claim 1, wherein
the clay is a non-swelling bentonite clay.
6. A stable, aqueous wax emulsion as set forth in claim 1, wherein
the amount of sulfuric acid is in the order of about 1/2 to about 1
percent by weight, based on the weight of the waxy material.
7. A stable, aqueous wax emulsion sizing composition consisting
essentially of a continuous aqueous phase; up to about 45 percent
by weight, based on the weight of the composition, of a crude scale
wax containing on the order of about 2 to about 10 percent by
weight oil content; about 10-15 percent by weight, based on the
weight of the wax, of non-swelling bentonite clay; and on the order
of about 1/2 to about 1 percent by weight, based on the weight of
the wax, of sulfuric acid.
Description
BACKGROUND OF THE INVENTION
This invention relates to the sizing of cellulosic products of a
fibrous nature to provide resultant products such as paper,
cardboard, insulation panels and low density wood fiber boards of
improved water-resistance. More particularly, the present invention
relates to a stable aqueous wax emulsion sizing composition for
producing such resultant products.
The usual procedure employed for sizing cellulosic products of a
fibrous nature is to contact an aqueous slurry of the fibers with
an aqueous dispersion of the size and then precipitate the size on
the fibers by adding a suitable precipitant or by contacting the
fibers with an emulsion sizing composition containing an organic
surface active emulsifier. Thus, for example, in the sizing of
paper pulp, the dispersion of size is generally added to the pulp
in the beater or Holland machine and it is then precipitated on the
fiber with paper maker's alum. Further for example, in the
manufacture of fiberboard from vegetable fibers such as wood fiber
or bagasse, the board or bagasse is formed from an aqueous slurry
on a forming machine which may be an Oliver or Fourdrinier or other
board-forming machine of conventional type well-known in this art.
The sizing agent is added to the aqueous slurry. The formed board
or mat, if to be used as a low-density soft-board or semi-hardboard
is then conventionally dried in a known manner. If the board or mat
is to be used as hardboard, it will additionally be processed under
extreme heat and pressure to develop high densities characteristic
of such product.
It is advantageous when employing the above methods of internal
sizing to use a sizing agent which may be prepared as a highly
concentrated, stable emulsion having a minimum amount of water.
This permits a saving on shipping and storage costs of the
emulsion.
Waxy materials are commonly included as a basic material for sizing
compositions due to the water-resisting properties characteristic
of them. However waxy materials are not definite and consistent,
particularly in the paraffin wax series, especially towards the low
end of this series, such as with the so-called "crude-scale wax."
This is particularly noticeable in that the wax composition, and
performance as a sizing ingredient, will vary from batch to batch;
and this has a consequent effect on the uniformity of resulting
emulsions. Crude scale wax is a non-crystalline wax on the low
order of the paraffin series of waxes, and the more refined grades
of this wax are stated to contain up to a maximum of 3% oils. This
value is highly variable, especially from batch to batch wherein
one batch may have one-half percent oil content while the next
batch may have 11/2 or 2 percent oil content. The melting point of
this more refined grade of crude scale wax material is about
125-140.degree.F. Lower grades of crude scale wax may contain up to
about 15 percent oil and have a melting point temperature of about
115.degree.F. The problem of wax consistency and uniformity from
batch to batch is not confined to crude scale wax, but this is one
commercial example in which the problem is most prevalent.
In emulsifying wax sizing formulations, a number of variably
successful approaches have been utilized including the use of clay
material alone as an emulsifier as well as more expensive
formulations including surface active agents of organic nature.
Although the afore-mentioned surface active type of emulsifiers
generally provide commercially acceptable sizing formulations, they
do have a number of disadvantages. For example, the surface active
agents are generally more expensive than the inorganic clay
emulsifier. When employing sizing compositions that require a
precipitant, it is frequently necessary to adjust the pH of the
pulp solution, and frequently to maintain a value from 4.5-5.5 for
best sizing results. The attendant greater acidic conditions cause
corrosion problems and furnish a medium favoring the growth of
certain types of plant life which cause slime and sludge
problems.
When utilizing a clay as the emulsifier for the wax, the effects of
the variations in wax uniformity and particularly oil content in
the waxy materials causes a high incidence of emulsification
problems. Quite frequently the resultant emulsion is not stable for
any length of time.
SUMMARY OF THE INVENTION
It is therefore one object and advantage of the present invention
to provide stable aqueous wax emulsion sizing compositions
utilizing a clay emulsifier.
Another object is the provision of stable aqueous wax emulsion
sizing compositions utilizing a clay emulsifier, which emulsions
are stable regardless of variation in the characteristics in the
wax from batch to batch.
A still further object is the provision of aqueous wax emulsion
sizing compositions that do not require the employment of organic
surface active agents or organic wetting agents in order to produce
highly stable emulsions.
Still another object is the provision of improved aqueous wax
emulsion sizing compositions which, although including a highly
acidic ingredient, do not require lowering of the pH much below
neutral.
The fulfillment of these and other objects and advantages of the
present invention are accomplished by an aqueous wax emulsion
sizing composition comprising a continuous aqueous phase; a waxy
material dispersed phase containing up to about 45 percent by
weight, based on the weight of the composition, of a wax; about
10-15 percent by weight, based on the weight of the waxy material,
of a clay; and a small amount, preferably about 1/2-1 percent by
weight, of sulfuric acid based on the weight of the waxy material.
In such an emulsion, the effects of the variations of wax
uniformity from batch to batch, and particularly oil content in the
waxy material, are inhibited from causing emulsification problems
and the resultant emulsion is highly stable over long periods of
time. Such emulsions can be used for the sizing of cellulosic
products of a fibrous nature to provide products such as paper,
cardboard, and low density wood fiberboard and insulation mats of
improved water-resistance by adding on the order of about 0.3% or
more by weight of the emulsion, based on the weight of the fiber,
at any convenient point to the aqueous pulp slurry such as by
addition to the head box, stock chest, mixing tank and the
like.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The wax component of the umulsion may comprise any form of
petroleum wax, and may therefore be present in the form of a
paraffin wax, scale wax or slack wax, as obtained from petroleum
distillation processes, petrolatum wax obtained from dewaxing heavy
lubricating oilstock or microcrystalline waxes obtained from the
petrolatum or from pipe still bottoms or other petroleum residue.
Petroleum waxes modified with various polymers such as polyethylene
or copolymers such as ethylene-vinyl acetate copolymers, and
similar polymeric materials or suitable natural waxes such as
beeswax, etc., and mixtures with the foregoing may also be
included. The waxes employed in the composition are preferably
petroleum waxes or, more preferably, scale waxes, especially those
of a crude nature. A principal objective of the present invention
is the capability of utilizing a wax ingredient of generally higher
oil content. Thus the scale waxes and especially crude scale waxes
are particularly pertinent for use in the present invention. Scale
wax and crude scale wax is generally the product of a petroleum
slop wax or slack wax that has been purged to the extent that it
still contains several percent of oil, generally 0.1 to 10 percent
or more. Most of the scale waxes produced have a melting point
generally of 126.degree.-130.degree.F ASTM melting point.
Thus the word wax is used in the present specification and claims
as used in its normal sense to designate any of the plastic,
amorphous or crystalline solid compositions generally denominated
as having a liquifying point between about 80.degree. and
180.degree.F, the capacity to acquire gloss when rubbed, low
viscosity at just above the melting point, low solubility and
solvency for fats at room temperatures and capacity to produce
emulsions with water. The compositions of the present invention
will improve the emulsification capabilities of any of the ordinary
materials customarily denominated as waxes, although the
compositions are most particularly preferred for increasing the
emulsification capability of waxes containing on the higher order
of oil contents.
The clay component of the composition may be any of those capable
of acting as an emulsifier for aqueous wax emulsions, although it
is preferred to use a clay that does not appreciably swell in
water. Preferably the clay will contain as a primary constituent a
mineral of the group known as montmorillonites; and such clays are
generally referred to as bentonites. The clay should be in a finely
divided state, generally with the particles having an average
particle size of around 200-300 U.S. Standard Tyler Mesh.
Substantial quantities of clay particles having a substantially
larger size are not recommended as generally tending to settle out
of the composition and thus tending to interfere with good
emulsification. The amount of the clay component employed in the
emulsification will generally be about 10-15 percent based on the
weight of the wax; although slightly more or less may be used but
without substantial further advantage. Considerably greater
quantities would not be economical and considerably lower
quantities would provide difficulty in emulsification.
The amount of water employed in the emulsification is not critical,
but should be sufficient to yield a fluid emulsion of the oil in
water type. As a practical matter, the final emulsion will
preferably contain about in the order of 50% water to insure that
the water is the continuous phase of the emulsion.
The concentrated sulfuric acid will be present preferably in an
amount of 1/2-1 percent based on the weight of the wax present.
Substantially lesser amounts will not provide the advantages of the
present invention. As the amount of concentrated sulfuric acid is
increased over about 1 percent based on the weight of the wax, the
concentrated sulfuric acid will have a greater effect on the pH of
the composition. It is generally desired that the pH of the
composition be maintained around a neutral pH; and about one-half
percent based on the weight of the wax will maintain the pH at
around 6-7. Any quantities of sulfuric acid much greater than 1
percent based on the weight of the wax will engender corrosion
problems without providing substantial improvement in
emulsification, unless special handling equipment is provided and
then the amount of sulfuric acid may be increased to on the order
of 5 percent or more.
At present it is not truly known exactly how the small amounts of
sulfuric acid are acting to improve emulsification and also provide
easy emulsification of heretofore non-emulsifying batches of
aqueous clay-wax dispersions. However it is presently theorized
that the small amounts of the highly electrolytic concentrated
sulfuric acid are acting upon the clay particles. The clay
emulsifier is a strongly ionizing material, and the electrical
forces associated with the clay particles apply a net negative
charge. It is theorized that the very small amounts of the strongly
electrolytic sulfuric acid tend to neutralize the electrical charge
on the individual plates within the clay crystal lattice to assist
the clay in more efficiently preventing wax droplets from
coalescing in the system and to maintain their dispersion in the
emulsion. In any event, it is found that by the present invention,
ease of emulsification between different batches of heretofore
difficult-to-emulsify waxes of variable oil content is greatly
increased. The resultant emulsions, on observation, contain much
smaller sized wax droplets than without the addition of the
sulfuric acid.
In the sizing operation, the concentrated emulsion is either
diluted to insure proper mixing in the pulp slurry or used as is
and metered in gradual increments into the pulp slurry. The in use
concentration, or dilution, of the emulsion is highly variable
depending on the degree of sizing effect desired. Generally the
emulsion can be diluted up to 100 fold for satisfactory sizing of
low density wood fiber board. No special precautions are necessary
with these emulsions either during storage or during the dilution
step other than to avoid freezing, and the emulsions will remain
stable indefinitely.
The sizing emulsion preferably is added to the aqueous pulp slurry
at the head box, stock chest, mixing tanks or other normal point
for addition of additives, wherein as a result of contact with the
cellulosic fibers the sizing constituents of the emulsion are
deposited on the fibers of the cellulosic products.
The emulsions of the present invention have been found to be
suitable for sizing of pulps known to the art as jute liner board,
sulfite pulp, sulfate and soda pulps, ground wood pulp and the like
to provide products such as paper, cardboard and wood fiber board
and insulation mats of all types. The emulsions are highly
effective for sizing low density wood fiber board and insulation
mats, but have a slightly deleterious effect on strength of greatly
compressed high density wood fiber hardboard.
EXAMPLES
The following specific examples will serve further to illustrate
the practice and advantages of this invention. In the following
examples, percentages listed are given on a weight basis, unless
otherwise stated References to ASTM methods are to the 1965 BOOK OF
ASTM STANDARDS published by the American Society for Testing and
Materials.
EXAMPLE I
The following example illustrates a preferred composition made in
accordance with the preferred method described hereinabove wherein
a small amount of concentrated sulfuric acid is added to a
crude-scale wax containing 3 percent oil content to produce a
stable emulsion having excellent sizing properties.
The sizing emulsion was prepared using a formulation, in parts by
weight, as follows:
Crude Scale Wax (Plasticrude 6005 brand by National Wax Co.) 100
grams Bentonite non-swelling clay (Panther Creek brand by American
Colloid) 15 grams Water 200 grams Concentrated Sulfuric Acid 1 gram
316 grams
The emulsion was formulated by adding the wax and clay to the
water; and then adding the sulfuric acid with constant mixing. The
mixture was first heated to about 180.degree.-200.degree.F. until
all of the wax was melted. The mixture was then agitated vigorously
until emulsification was completed, as by agitation in a high shear
mixer for approximately 10 minutes.
A low density (about 10-15 lb.) wood fiber board was made by
forming an aqueous slurry of the wood fibers and diluting with
water to about a 1% consistency. The fiber slurry was thoroughly
mixed and the above sizing emulsion was added in an amount of about
0.5 percent based on the weight of the wood fiber solids; and
mixing continued. Then paper maker's alum was added in an amount of
about 0.5 percent based on the weight of the emulsion sizing
composition solids; and mixing continued. The thoroughly mixed
aqueous slurry was formed into a mat on a forming machine; lightly
pressed to expel additional water and dried in an oven to produce
the softboard. The finished board had low water absorption
properties.
EXAMPLE 2
In a plant-size production evaluation, a number of batches of wax
emulsions were made using 615 lbs. of a scale wax, 1230 lbs. of
water and from 95 to 120 lbs. of a non-swelling bentonite clay. The
emulsions were made by adding the wax to the water and then heating
this mixture to 200.degree.F until there was complete melting of
the wax. Then mixing was commenced and increased to vigorous
agitation at which point the clay was added. Mixing was continued
for an additional 15 minutes, at which time emulsion samples were
taken and evaluated for capability of mixing with cold water.
It was found in approximately 20 percent of the batches that the
emulsion, when cooled down to about 125.degree.F, broke and formed
a skin of unemulsified wax particles on the surface or contained
large clumps of unemulsified wax particles. By analyzing the waxes
from the various batches, it was found that in the satisfactory
batches the wax had an oil content of about 0.1-0.2 percent and a
melting point of about 140; while in the unsatisfactory batches the
oil content was generally about 2 percent or higher and the average
melting point was about 127.degree.F.
EXAMPLE 3
To the unsatisfactory batches obtained in EXAMPLE 2 was added
approximately 0.15 percent sulfuric acid based on the amount of wax
present in the particular emulsion. As a control measure, aliquots
of the unsatisfactory batches did not receive sulfuric acid
addition. In comparison, all of the batches which received the
sulfuric acid now mixed well with cold water, had excellent
emulsion appearance and were storage stable; while the control
aliquots continued to form a skin of unemulsified wax particles, or
clumps of unemulsified wax particles and generally did not maintain
stable emulsification. Further the control aliquots were difficult
to re-emulsify without heating and addition of more clay along with
strenuous agitation.
It was further observed that the aliquots containing sulfuric acid
appeared to have a much finer particle size of the wax and the
emulsion. Although analytical particle size measurements were not
taken, the batches containing sulfuric acid were much lighter in
color; and this lightness in color is a general indication of the
fineness of the wax particle and the wax emulsion. In contrast, the
aliquots not containing sulfuric acid were quite dark in color,
generally indicating large particle size of the wax particles.
EXAMPLE 4
A series of low density wood fiber insulation mats were made and
compared for 2-hour water absorption properties by the method set
forth in ASTM C209. In all instances the sizing emulsion was added
in an amount of 1 percent by weight of the solids in the insulation
mat, and the insulation mats were identical with the exception of
the character of the sizing emulsion, as follows:
Two-Hour Sizing Emulsion Water Absorption
______________________________________ 33% crude scale wax (2% oil)
+ 15% Bentonite clay 4.7% 33% crude scale wax (2% oil) + 15%
Bentonite clay + 1/2% H.sub.2 SO.sub.4 3.7% standard commercial
rosin size 5.0% standard commercial asphalt emulsion 4.5%
______________________________________
EXAMPLE 5
Two different batches of crude scale wax were compared for emulsion
quality and stability by observation over a 48-hour period and also
for 2-hour water absorption by method ASTM C209.
One batch of the crude scale wax (hereinafter identified as WAX A)
had an oil content of 2 percent and a melting point of
125.degree.F. The second wax sample (hereinafter identified as WAX
B) had an oil content of 9.1 percent and a melting point of
118.degree.F. Aliquots of these different waxes were formed into
emulsions containing 30.7 percent wax, 15 percent clay and 55
percent water. Mats of pine furnish were also made using these
emulsions, the emulsions were added to the furnish in an amount of
0.5 percent, and the mats evaluated for water absorption by method
ASTM C209.
For evaluation of emulsion quality and stability by observation,
the following rating scale was applied:
Excellent = The emulsion rapidly diluted with cold water without
forming oil spots or a wax film on the surface of the emulsion,
without the formation of a third phase, and without breaking.
Good = The emulsion was easily and thoroughly diluted with cold
water, forming only a few small oil spots, without breaking or
forming a third phase and without observable coalescence of wax
droplets.
Poor = The emulsion broke, or formed a third phase, or would not
dilute with cold water without extensive coalescence of wax
droplets.
Exemplary results of these evaluations with varying amounts of
sulfuric acid addition to the different crude scale wax batches are
as follows:
Observed 24-Hour Water Formulation Emulsion Quality Absorption
______________________________________ WAX A Good 15.4% WAX A +
1.5% H.sub.2 SO.sub.4 Excellent 7.5 - 7.9% WAX B (high oil content)
Poor 7.2% WAX B + 0.5% H.sub.2 SO.sub.4 Good 7.9% do. 1.0% do. Good
+ 7.5% do. 1.5% do. Excellent 7.5% do. 5.0% do. Excellent 7.4%
______________________________________
While the present invention has been described and exemplified with
respect to certain embodiments, it is not to be considered limited
thereto; and it is understood that variations and modifications
thereof, obvious to those skilled in the art, may be made without
departing from the spirit or scope of this invention.
* * * * *