Note: Descriptions are shown in the official language in which they were submitted.
~ 1
TITLE
POLYVINYL ALCOHOL BASED WAX-FREE SIZE COMPOSITION
BACKGROUND OF THE INVENTION
.
Field of the Invention
T}-is invention relates to size compositions
and more specifically it relates to polyvinyl alcohol
based size compositions containing low ethylene oxide
adduct additives.
Description oE the Prior Art
Spun warp yarn must be sized with a
water-soluble polymer which provides it with a
protective surface coating; the latter is required
during the weaving of the yarn into fabric. After
weaving the greige fabric produced must be stripped
of the protective coating by desizing before it can
be subjected to various finishing operations and in
particular to dyeing. Sizes based on polyvinyl
alcohol or combinations of polyvinyl alcohol and
starch must generally be used with a wax additive
present in the formulation to minimize drier drum
sticking in the slasher during application of the
size. These wax additives are difficult to remove
from the greige fabric during desizing, often
requiring extraction by special solvents as well as
higher desize bath temperatures. As a consequence
the finishing mill is faced with higher production
costs due to greater process complexibility, higher
energy costs and a higher percentage of second
quality greige fabric.
The use of polyvinyl alcohol-based sizing
solution containing a small amount of quaternary
ammonium salt or a quaternary imidazolinium salt is
disclosed in U.S. Patent No. 4,333,063; these
additives provide good operability in the absence of
AD-5409 35 wax and result in fabric exhibiting improved
12~14~
finishing performance. However, such formulations
have the serious deficiency of frequently exhibiting
a non-reproducible sizing performance; the latter is
due to an erratic and unpredictable removal of the
cationic additive by inter-action with anionic
contaminants which tend to accumulate in the sizing
solution. The primary source of these anionic
contaminants is the spun yarn being sized.
The incorporation into polyvinyl
alcohol-based sizes of very low levels (maximum of
0.05 wt. % based on polyvinyl alcohol) of low
ethoxylate adducts of linear alcohols as defoaming
agents is disclosed in U.S. Patent No. 4,251,403;
such material$ have been found to be ineffective as
wax substitutes and therefore are not used as
substitutes for wax in wax-free warp sizing
compositions.
Summary of The Invention
According to the present invention, there is
provided a composition consisting essentially of (a)
from about 45.5 to about 99.9~ by weight of vinyl
alcohol polymer selected from the group consisting of
polyvinyl alcohol, vinyl alcohol/methyl methacrylate
copolymer, and polyvinyl alcohol containing
solubilizing comonomers other than methyl
methacrylate, said vinyl alcohol polymer having a
saponification number of from about 1 to about 160
and a 4 percent solution viscosity of from
about 3 to about 70 mPa-s at 20C;
(b) from about 0.1 to about 3 percent by
weight of liquid nonionic low ethylene oxide adduct
of branched alcohol or mixture of branched alcohols
wherein the average ethylene oxide content is from
about 1 to about 7 units and the alcohol has an
average carbon content of from about 8 to about 18
carbon atoms;
~ '7~3~4~
(c) from 0 to 49.9 percent by weight of
starch;
(d) from 0 to about 5 percent by weight of
ethylene oxide oligomer having a molecular weight
S (number average) of from about 200 to about 800 and
(e) from 0 to about 49.9 percent by weight
of carboxymethyl cellulose,
(f) from 0 to about 1 percent by weight of
at least one auxiliary ethylene oxide adduct selected
from the group consisting of low ethylene oxide
adduct ~containing an average ethylene oxide content
of from about 1 to about 7 units) of a linear alcohol
or of a mixture of linear alcohols (havlng an average
carbon content of from about 8 to about 18 units) and
medium to high ethylene oxide adduct (containing an
average ethylene oxide content of from about 8 to
about 40 units) of linear or branched alcohols
(having an average carbon content of rom about 8 to
about 18 units) provided the combined weiyht of
starch and carboxymethyl cellulose does not exceed
the weight of vinyl alcohol polymer.
Further according to the present invention
there is provided a concentrate of the low ethylene
oxide adduct blended with vinyl alcohol polymer, a
wax-free aqueous size solution comprising the
composition of the present invention having a solids
content of 2-20% by weight, process for sizing
filament yarn with wax-free aqueous solution and
sized yarn comprising spun yarn having a wax-free
protective surface coating of the composition of the
present invention.
As used herein, the term "consisting
essentially of" means that the named ingredients are
essential, however, other ingredients which do not
prevent the advantages of the present invention from
being realized can also be incl~ded.
7~
Detailed Description of the Invention
It has been found that the addition of a
liquid, nonionic, low ethylene oxide adduct of a
branched alcohol, in the amount of 3 percent or less,
to the vinyl alcohol polymer based size composition
eliminates sticking of the sized yarn on the drying
cans in the slasher, provides excellent weaving
efficiency, and easy size removal under mild desize
- conditions, yielding desized greige fabric that
exhibits excellent dye receptivity. Size
compositions of the present invention are recommended
for use in the conventional sizing, heat setting and
aqueous desizing operations presently employed by
spun yarn textile mills.
For the purposes of the size compositions of
the present invention the vinyl alcohol polymer can
have a saponification number (mg KOH to neutralize 1
g polymer) of from about 1 to about 160 and a 4
percent solution viscosity of from about 3 to about
70 mPa-s.
Examples of suitable vinyl alcohol polymers
include:
(a) Fully hydrolyzed vinyl alcohol/methyl
methacrylate copolymer (containing from about 3.5 to
about 6 mole percent methyl methacrylate) having a
viscosity of from about 3 to about 60 mPa-s (measured
at 20C using a 4 percent aqueous solution). Such
copolymers can be produced by the alcoholysis of a
vinyl acetate/methyl methacrylate copolymer;
(b) Partially hydrolyzed polyvinyl alcohol
containing from about 4 to about 12 mole percent of
vinyl acetate having a viscosity of from about 3 to
about 60 mPa-s;
(c) Fully hydrolyzed polyvinyl alcohol
having a viscosity of from about 3 to about 70 mPa-s
` 5
(d) Polyvinyl alcohol containing
"solubilizing comonomers" other than methyl
methacrylate (such as methylacrylate, methyl hydrogen
maleate;
(e) Various mixtures of the above vinyl
alcohol polymers.
The nonionic additive of the present
invention is a low ethylene oxide adduct (containing
- an average ethylene oxide content of from about 1 to
about 7 units) of a branched alcohol or a mixture of
branched alcohols (having an average carbon content
of from about 8 to about 18 units). The preferred
makeup of this additive is an adduct containing from
about 2 to about 5 ethylene oxide units with a
branched alcohol containing an average of from about
10 to about 15 carbon atoms. The most preferred is
one consisting of an average of about 3 ethylene
oxide units with a branched alcohol containing an
-average of about 13 carbon atoms. ~ergitol* 15-S-3,
?O a product manufactured by~Union Carbide, represents
- this most preferred additive.
~ The amount of vinyl alcohol polymer in the
composition of the present invention is from about
45.5 to about 99.-9 percent by weight. The preferred
range is from about 63 to about 99.8 percent and the
most preferred range is from about 72.7 to about 99.6
percent. In typical polyvinyl alcohol-based size
formulations, the higher the polyvinyl alcohol
content of the size, the higher will be the weaving
efficiency exhibited by the sized yarn. In general
size add-on requirements are reduced progressively as
the polyvinyl alcohol content of the size is
increased.
The amount of the nonionic additive of the
present invention is from about 0.1 to about 3
*denotes trade mark
~ `` 6 ~ ~ 7~
percent by weight. About 0.1 weight percent additive
is necessary to give significant drier drum release,
while greater than about 3 weight percent may result
in reduced weaving efficiencies. A preferred range
of additive is from about 0.2 to about 1.5 weight
percent with which most of the benefits of the
present invention can be achieved. The most
preferred concentration range of additive is from
- about 0.4 to about 0.8 weight percent; compositions
containing this level of additive give the best
balance of drum deposit performance, abrasion
resistance and dye receptivity after desizing.
Optionally, starch can be incorporated in
the size compositions of the present invention in an
amount of up to about 49.9 weight percent. Up to
this level of starch the benefits of the no-wax
additive of the present invention are clearly
evident. The preferred starch limit is up to about
33 weight percent, while the most -preferred starch
limit is up to about 25 weight percent. In the most
- preferred vinyl alcohol polymer~starch blends the
~ effectiveness of the nonionic additive of the present
invention approaches that observed with compositions
containing vi-nyl alcohol polymer as the sole
polymeric component. A variety of types of starch
and derived starch will function as optional
additives in the composition of this invention.
These include Kofilm* 50, [an acetylated starch
product supplied by National Starch], as well as
Astrogum* 3010 [a medium viscosity sodium
carboxymethylated starch] and "Astrogum" 3020 [a low
viscosity sodium carboxymethylated starch], which are
products supplied by Penick and Ford.
Carboxymethyl cellulose (CMC) can also be
used as an optional ingredient in the composition of
*den~tes trade mark
the present invention in an amount of up to about 50
wt. %, preferably up to about 33 wt. %, and most
preferably up to about 25 wt. %.
The combined weight of the starch and CMC
ingredients should not exceed the weight of the vinyl
alcohol polymer present in the composition.
- Another optional additive is a low to medium
molecular weight (200-800 number average) oligomer of
- ethylene oxide often added to vinyl alcohol polymer
,as a dedusting agent. U.S. Patent No. 4,389,506
describes the use of 3 weight percent of Carbowax*
600, a product of Union Carbide, as yielding the most
preferred dust-free product. Concentrations up to
about 5 weight percent ~Carbowax" 600 result in only
minor reductions in the benefits derived from the
presence o the nonionic additive of-the present
invention and represents the upper additive level
recommended. A preferred upper limit is 3 weight
percent while the most preferred upper limit of this
type of additive is 1.5 weight percent. At the most
- preferred upper concentration the benefits derived
~ from the nonionic additive of the present invention
can be almost fully realized.
Further optional additives can be auxiliary
low ethylene oxide adducts (containing an average
ethylene oxide content of from about 1 to about 7
units) of a linear alcohol or of a mixture of linear
alcohols (having an average carbon content of from
about 8 to about 18 units) or medium to high ethylene
oxide adducts (containing an average ethylene oxide
content of from about 8 to about 40 units) of linear
or branched alcohols (having an average carbon
content of from about 8 to about 18 units). These
additives can be present in the composition of the
present invention in low concentrations, i.e. up to
about 1 wt. percent.
*denotes trade mark
4~
The aqueous size solution of the present
invention will generally have a solids content of
from about 2 to about 20 weight percent. The
preferred size bath solids content is from about 5 to
about 15 weight percent while the most preferred
formulation contains from about 7 to about 12 weight
percent since this level of solids in most cases will
provide sufficient size adcl-on to give the sized yarn
adequate abrasion resistance. The aqueous polyvinyl
alcohol based size solution is considered to be
unique because it does not contain a wax additive
which must be present under normal mill conditions.
The aqueous size solution is prepared by
slurrying polyvinyl alcohol with water at ambient
temperature. The nonionic additive along with any
optional additives are then introduced. The
subsequent mixture is heated with stirring at about
77C until complete solution has been achieved.
The size solution of the present invention
can be prepared directly from a blend of vinyl
alcohol polymer with a low amount of the nonionic
additive of the present invention. The polyvinyl
alcohol/nonionic additive mixtures of this invention
are produced by dry blending a variety of polyvinyl
alcohol and the additive(s) under high intensity
mixing conditions at a temperature at which the
additive component(s) will be liquid(s). Moreover,
if more than one nonionic additive is used, the
latter can be preblended and added as a single
component. For example, using a Readco* Sigma Blade
mixer manufactured by the Read Co., York, PA,
polyvinyl alcohol and "Tergitol" 15-S-3 or "Tergitol"
15-S-3/"Carbowax" 600 mixtures were converted int~
homogeneous blends by mixing for about 30 minutes at
a temperature above about 20C. This mode of
* denotes trade mark
7~
preparation is carried out by slurrying in water at
ambient temperature the required amount of vinyl
alcohol polymer/nonionic additive blend to give the
desired size bath solids. The resulting mixture is
then heated with stirring at a temperature of about
77C until complete solution has been achieved.
The size solution of the present invention
can also be produced by using a concentrate of the
- nonionic additive of the present invention in a vinyl
alcohol polymer. The concentrate consists
essentially of from about 45 to about 90 percent by
weight of vinyl alcohol polymer and from about 10 to
about 55 percent by weight of the liquid, nonionic
low ethylene oxide adduct additive of the present
invention. Optionally, the concentrate can contain
up to about 45 percent by weight of starch, up to
about 45 percent by weight of Carbowax, up to about
45 percent by weight of carboxymethyl cellulose and
up to about 45 percent by weight of low ethylene
oxide adduct of a linear alcohol or mixture of linear
alcohols or medium to high ethylene oxide adduct of
linear or branched alcohols. The concentrate is used
to produce the size composition of the present
invention by adding it in the required amount to a
preformed vinyl alcohol polymer solution. Use of
such a concentrate can provide a unique and
surprising advantage. Normally when vinyl alcohol
polymers are added even with vigorous agitation to
hot aqueous solutions, the vinyl alcohol component
fuses upon contact with the hot water and becomes
very difficultly soluble. In contrast the above
described concentrate, if it contains at least about
30~ by weight of the nonionic additive of this
invention, is relatively easy to disperse when added
directly to hot water. The most preferred nonionic
1~79~4~
additive level is from about 40% to about 50%. Above
about 50% the vinyl alcohol polymer tends not to
absorb all of the additive. Use of the above
described concentrate provides the highly desirable
advantage of permitting rapid readjustments in the
level of the nonionic additive of the present
invention in a given hot size bath to match specific
mill requirement.
Preferably, the above referred to
concentrate contains from about 45 to about 70
percent by weight of vinyl alcohol polymer, from
about 30 to about 55 percent by weight of nonionic
additive, up to about 20 percent by weight of starch,
up to about 20 percent by weight of Carbowax, and up
to about 20 percent by weight of carboxymethyl
cellulose. Most preferably the concentrate will
contain from about 50 to about 60 percent by weight
of vinyl alcohol polymer, from about 40 to about 50
percent by weight of nonionic additive, up to about 5
percent by weight of starch, up to about 5 percent by
weight of Carbowax and up to about 5 percent by
weight of carboxymethyl cellulose.
The size is applied to the yarn web or sley
using a slasher. The latter is equipped with a
heated size box containing the size formulation. The
unsized sley is sized by being drawn through the hot
size solution, through squeeze rolls to remove excess
size solution, over a series of heated drying drums,
through a bust bar assembly to separate the sley into
individual warp ends and finally onto a beam for
collection. When the required amount of sized sley
has been collected on the beam, the latter is
installed in a loom where the yarn is woven into
greige fabric.
~ 314~1.
~ he sized spun yarn produced using the size
composition of the present invention has a wax-free
protective surface coating and exhibits the unique
property of providing excellent weaving performance
despite the absence of wax in the vinyl alcohol
polymer based size. Moreover the greige fabric
produced being wax-free, is readily desizable under
mild desize conditions yielding a desized fabric with
excellent dye receptivity. Desizing is carried out
by passing the sized greige fabric through an
alkaline scour bath followed by several hot water
(about 65-35C) rinses. Fabric prepared with
conventional wax-containing sizes requires much more
stringent scouring and rinse conditions than are
required with the size formulations of the present
invention. A high level of removal of the size
components from the greige fabric is required prior
to its processing in the finishing mill so as to
permit efficient and reproducible dyeing as well as
other finishing operations on the fabric. Both the
no-wax sized yarn and the no-wax greige fabric
produced from it are thus considered to be unique.
The no-wax size composition of the present
invention is especially suited for use with
polyester/cotton spun yarn blends. It is
particularly useful for 65/35, 50/50 and 40/60
polyester/cotton spun yarn blends. The size
composition also has utility for 100% cotton spun
yarns.
Incorporation of the no-wax additive of the
present invention into vinyl alcohol polymer based
size formulations permits the elimination of wax as
an additive, making feasible the preparation of sized
yarn exhibiting excellent slashing and weaving
characteristics suitable for producing a variety of
12
types of fabrics under typical weaving conditions
(e.g. involving shuttle, airjet, rapier looms). The
derived fabrics, being wax-free, are characterized by
easy size removal and the desized fabric exhibits
superior dye receptivity.
The following examples are given for the
purpose of illustrating the present invention. All
parts and percentages are by weight unless otherwise
- specified.
Examples
i Sizing solutions were prepared in a
steam-jacketed kettle by adding the vinyl alcohol
polymer to the requisite amount of ambient
temperature water to obtain the desired size bath
solids. The temperature of the slurry was brought to
` - 77C with stirring. Any additives to be tested in
the for~ulation were added at this point.
The resulting size solution was used to size
24 ends of a polyester-/cotton spun yarn using a
~allaway Slasher* Model 51 manufactured by West
- Point Foundry and Machine Co.-operated at 10
~ meters/minute using pressure at the squeeze roll.
After the yarn had been s`ized, the size add-on was
measured by-weight loss after extraction of the sized
yarn with boiling water. Assessment of the
performance of the size formulation during slashing
as well as characterization of the sized yarn itself
was carried out using the following test procedures.
(a) Drum deposits
The extent to which deposits form on the
No. 1 drying drum in the slasher is related directly
to the tendency of a given size formulation to cause
sticking of the individual warp ends to the drying
drums in the slasher. Thus the effectiveness of a
; 35 release agent added to the size formulation to
*denotes trade mark
12
14~
minimize yarn sticking in the drying section of the
slasher can be measured accurately. Operating the
Callaway slasher under the conditions described above
and setting the temperature of the No. 1 drying drum
at 190C and the remaining three drums at 220C, the
amount of deposit accumulating on the No. 1 drum will
reach an equilibrium value in about one minute. Once
equilibrium is achieved the deposits on this drum are
removed quantitatively with a rubber squeegee during
one complete revolution of the drum; the deposit is
then dried and weighed. The amount of deposit
collected provides a direct measure of a size
formulation's performance, namely the yreater the
amount of drum deposit, the greater the tendency the
formulation has to cause drying drum sticking. Of
the various all vinyl alcohol polymer based size
formulations evaluated during the course of this
study, the highest drum deposit was observed with
unmodified PVA No. 2 (a fully hydrolyzed vinyl
alcohol/methyl acrylate copolymer having a 4%
solution viscosity of 13.5 mPa.s and a saponification
number of 40). In each example cited, the actual
drum deposit value observed and a rating
proportionated against the PVA No. 2 value (unless
noted otherwise) are given. A rating of 0.200 or
lower is considered necessary for operability under
typical mill conditions of a 100% vinyl alcohol
polymer size.
(b) Abrasion resistance of the sized yarn
is determined using a laboratory abrasion tester.
The test method employed consists of stringing 21
ends of sized yarn through a section of conventional
weaving loom reed and applying controlled tension to
each individual warp end. The reed is made to
oscillate against the warp ends at one cycle/second
14
and the number of cycles required to cause the
breakage of each end is recorded. A second set of 21
ends is next tested in the same manner. The two sets
of data obtained are then statistically averaged so
as to give the number of cycles required to cause 50%
breakage of the warp ends used in the test. This
quantity in cycles is referred to as the F50 rating
for a given size formulation.
- Abrasion resistance is highly dependent upon
size add-on. For comparatlve purposes all F50 data
must be normalized to a given size add-on, namely,
10%. This is preferably done by obtaining F50
values at six or more add-ons for a given size
formulation and subjecting the resulting data to a
linear regression analysis. All F50 data reported
in the characterization of the various examples cited
have been treated in this manner. A maximum F50
value was observed for size formulations prepared
with PVA No. 1 (a fully hydrolyzed vinyl
alcohol/methyl methacrylate copolymer having a 4%
solution viscosity of 28 mPa.s and having a
saponification number of 30). In all examples cited
the actual F50 value observed and a comparison
rating with the PVA No. 1 size (unless otherwise
noted) are given; the latter was calculated by
setting at unity the log F50 value of the PVA No. 1
size at 10~ size add-on and proportionating against
it the log F50 value observed at 10% size add-on
for the size formulation in the example. At 10%
add-on a rating of 0.875 or higher is considered to
be a requirement for operability under typical mill
conditions using a 100% vinyl alcohol polymer size.
(c) Dye receptivity
Sized yarn to be used in this test is first
heat set by passing it through an oven at 200C with
.
`~ 15 ~Z ~
a holdup time of 45 seconds. The heat-treated yarn
is then desized under mild conditions consisting of
soaking the yarn for 15 seconds at 55C in a 0.5%
Alkanol WXN*(a modified sodium alkylaryl sulfonate
supplied by E. I. du Pont de Nemours and Company)
solution followed by rinsing the yarn for 45 seconds
at 75C three times. After passage through a wringer
the yarn is dried thoroughly. Using the dried,
desized yarn its dye receptivity is determined by
measuring the time in seconds for an aqueous solution
of Chemurgy green dye to penetrate one inch up a hank
of dry yarn. The poorest dye receptivity was
observed using PVA No. 1 containing 8% Synchem* 110
-wax (a solid hot water dispersible tallow wax,
supplied by Milliken). Setting this value at unity
all other dye receptivity values for the exa~ples
cited have been proportionated against it. Thus in
each exa~ple given both the observed dye receptivity
as well as a dye-receptivity rating are reported. A
rating of 3.5 or higher is considered to be necessary
- to achieve good dye receptivity under normal mill
conditions.
Examples 1 and 2 and
- Comparative Examples 1 and 2
A sizing solution based on PVA No. 2
containing 0.4~ "Tergitol" 15-S-3 (Ex. 1) was tested
at 12 size add-on levels ranging from 5-15~ (based on
yarn weight) and compared with similar formulations
prepared with PVA No. 2 alone (Ex. C-l), PVA No . 2
containing 8% ~Synchem" 110 wax (typical mill
formulation) (Ex. C-2), and PVA No. 2 containing 0.4
Tergitol 15-S-3 and 1.5% "Carbowax"600 (Ex. 2).
Results are summarized in Table I.
*denotes trade mark
-
r~
~1 C In ~U~
~._, ~ ~o
.,_1 V
~; U~
V
u~
~ ~ro
O-- ~
~ ~ ~ro O
c ~ ~no O~
C ~1 ~ ~O~ ~D
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.rl O ~ OO O O
U~ C X
4 '15 _
~ ~ o U~
I
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j_~ ~4 0 ~
R u~ V o
O ~ 10 o
Q.
a
~- ~ ~ CO
Ul ~
4~ _l ~D O --I
C~ O-- ~ dP
n
r
O ~ ~ _ ~ ~I X
~ O ~ O +
~ ~ a~ x J~ 3
.,1O d~-r1 ~ OO ~ O dP r~ ~ O
U~ Z ~ ~ I ZZ V 3 Z ~ ~Jl I .n
O ~ 4 U~ dP C 4 U~ 4
~1 A: O ~ OD ~t O ~¢ O ~
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17
As can be seen from the above data, ~xamples
1 and 2, which represent embodiments of the present
invention, provided yarn having acceptable
combinations of the three key performance features,
comparative Examples 1 and 2 were unacceptable
because in C-1 the drum deposit was too high, and in
C-2 the dye receptivity was extremely poor.
Examples 3 and 4 and Comparative Examples 3 and 4
- A sizing solution based on PVA No. 1
containing 0.4% "Tergitol" 15-S-3 (Ex. 3) was
evaluated at 12 size add-on levels falling in the
range of 5-15% (based on yarn weight) and compared
- with similar form~lations based on PVA No. 1 alone
(Ex. C-3), PVA No. 1 + 8% "Syncheml' 110 wax (typical
mill formulation (Ex. C-4) and PVA No. 1 containing
0.4% "Tergitol" 15-S-3 and 1.5% "Carbowax" 600 (Ex.
4). Results are summarized in Table II.
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v ~ ~ ~ o ~`
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~ x
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c~ ~
v~ -
a)- o ~ ~ ~ c~
u~ ~r ~r
o - ~
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Lr~
c ,~ a~ o ~ o~
o c~ JJ
o ~ o o
a
~ v
r/ ~ u~ ~ o o
u~ ~ ~ ~ u~
a~- o a~ ~D O ~D
o ~ 0 ~ ~ ~ ~ ~l
~u~ ~ o
E~ 0--
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Qv ~: ~ cr~ o 'r
~.,~ o ~ o o
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u~
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e = : ,,
O ~ -E~ ~ o X
JJ J ~ X V 3
._~ O d~-~ ~ O O S ~ao d~ o
u7 Z '1~ ~ I Z Z ~.) 3Z 'i~
O U U~ d~ C L~
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e
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18
- 12~14~
`` ., 19
The above data illustrate that the same
advantages reported in Examples 1 and 2 could be
realized using the additive of the present invention
with an alternative grade of vinyl alcohol polymer.
Example 5 and Comparative Exam~les 5 and 6
This set of examples employed a 75/25 blend
- of Yinol* 425/"Vinol" 205 polyvinyl alcohols
supplied by Air Products. "Vinol" 425 is an
intermediate hydrolyzed (94% by weight hydrolysis)
and "Vinol 205 is a partially hydrolyzed (88% by
weight hydrolysis) PVA grade. A sizing solution
containing this blend of polyvinyl alcohols with 0.4~
"Tergitol" 15-S-3 present (Ex. 5) was evaluated at 12
size add-on levels ranging from 5-15% (based on yarn
weight) and compared with similar formulations
- prepared with the unmodified blend (Ex. C-5) and with
the blend containing 8% nSynchem" liO wax (Ex. C-6).
The results are summarized in Table III.
*denotes trade mark
19
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.,, JJ ~ ~r o
r~ XU~ I
a) v
a a~
C~ O C~
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CLr o~ ~
C ~ ~ ` 3: 1_
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~o C ~; o o o
r~
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U~
U~ ~ ~1co
Ln ~ a~
o ~ U~ :~
~ u~ Qo ~
Q O~ o
Q~ ~o ~i o
a
a~
U~ ~ ~ ~ o
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a o ~
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o ~ o : ~ o ~ O O
.,, ~ ~ ~ ~r ~ ~ ~ c
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.,, :: ~ == ::tnx
O Ln O O ~ ~ ) L!~ O O U~ O 0 3
C C ~ U~ ~ C ~ ~ C ~ dP
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21
As can be seen from the above data, the
additive of the present invention provided the same
advantages with compositions based on intermediate
and partially hydrolyzed polyvinyl alcohols as was
observed with the vinyl alcohol polymer compositions
described in Examples 1, 2, 3 and 4.
Example 6 and Comparative Examples 7 and 8
A size formulation containing a 75/25 PVA
- No. 2/"Kofilm" 50 starch blend, 0.4% "Tergitol"
15-S-3 and 1.5% "Carbowax" 600, (Ex. 6) was evaluated
at 12 add-on levels ranging from 5-15% (based on the
yarn weight) and compared with a similar formulation
containing no additives (Ex. C-7) as well as one with
8% "Synchem" 110 wax (Ex. C-8) present. The results
are summarized in Table IV.
12~ 3L4~
22
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-~ 23
The above data showed that the additive of
the present invention in PVA/starch based systems
significantly reduces the drum deposit and increases
the dye receptivity of the yarn. The adverse effect
of the additive of the present invention on abrasion
resistance was observed to be no greater than that of
"Synchem" 110 wax.
Example 7 and Comparative Examples 9 and 10
- A size formulation derived from a 50/50 PVA
No.2/"Kofilm" 50 starch blend and containing 0.4%
"Tergitol" 15-S-3 and 1.5% "Carbowax" 600 (Ex. 7) was
evaluated at 12 size add-on levels ranging from 5-15%
(based on yarn weight) and compared with a similar
size formulation containing no additives (Ex. C-9) as
well as a formulation with 8~ "Synchem" 110 wax (Ex.
C-10) present. The results are summarized in Table V.
23
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24
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C ~ ~ ~0 0 ~ X
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, C ~ O ~ O
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O ~ ~ ~ ~9
Lr ~ ~
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a~
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t)
- ~ ~ ~ o~ ~:
a ~ ~J .
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v O ~ o -( ~ o o ~ o ~
u~ o z-~ ~ I ~ o z ~ o z ~ 3 .C
o u~ ~ + ~ ~n dP ~ U~ ~UU~ ~ dP J'
o ~ o ~ ~ o ~ ~ o co o
E o ~ Y o E~ u~ o o o ~ 4~ o ~
O U~ + ~ C
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a
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~7~14~
_ 25
As shown by the above data the additive of
the present invention provided beneficial effects
when used with 50/50 vinyl alcohol polymer/starch
blends in both drum deposit performance as well as in
dye receptivity. The additive reduced abrasion
resistance to approximately the same extent as did
the nSynchem" 110 wax additive.
Comparative Examples 11-13
- Size formulations based on PVA No. 2 were
prepared with several low ethylene oxide adducts of
linear alcohols namely "Tergitol" 25-L-3, Alfonic*
- 1012-40 and ~Alfonic" 1412-40 (Ex. C-ll to 13).
Data characterizing the low ethylene oxide
adducts is summerized in the Table below.
15Hydrophobic Ethylene Oxide
- Product Mol Wt. No Carbons Moles - Wt. %
nAlfonic" 170 C 10.9 2.5 40
- 1012-40
-nAlfonic" 206 C-13.4 3.0 40
201412-40
- nTergitol" 200 C 13 3.0 37
15-~-3
"Tergitol" 200 C 13 3.0 37
25-L-3
The hydrophobe is a linear alcohol in the "Alfonic"
products and in ~Ter~itol" 25-L-3 but is secondary
alcohol in "Tergitoln 15-S-3. The above Table shows
that "Alfonic" 1412-40 and "Tergitol" 25-L-3 are an
almost exact linear counterparts of
"Tergitol" 15-S-3. The "Alfonic" products are
supplied by Conoco and the "Tergitol" products are
supplied by Union Carbide.
Table V~ shows the composition and
properties of size formulations prepared with the
above linear alcohol derived ethylene oxide adducts
as well as with the additive of the present invention
(Ex. 1).
*denotes trade mark 25
7~
26
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V ~ o ~ o
r~ O dQ ~I ~ dD O O o`P e ~ d~ o o d~ e ~ o o ~ o
u~ z~ rJ I o~æ~ o I om Z~r o I o~ z~ ~ I om
O Ll ~ ~ X ~( ~ ~ ~
~ ~'S ~ I ~ ¢ ~ ~ ~ ~ ~--I ~ ~ ~ ~ I ~ ~
E ~ o ~ ~: o C.) o ~ ,cs ~ ~ o ~ ~ o
O ~, +: ~ + ~+ = ~ + ~ +: ~ + ~ ~9 t4 +: ~ +: ~D
E _I ~1 ~1
115
~L2~L4~
27
As can be seen from the above data, the
formulations (Ex. C-ll to 13) containing a linear
alcohol-based additive gave significantly inferior
drum deposit and abrasion resistance performance than
were observed when the additive of the present
invention was used.
Examples 8-10 and Comparative Examples 14-20
Size formulations were prepared with PVA
No. 2 modified with a range or "Tergitol" 15-S
products containing from 3 to 40 ethylene oxide units
ti.e. "Tergitol" 15-S-3 to "Tergitol" 15-S-40). The
: level of the "Tergitol" additive was 0.4 wt. %, and
3.0~ "Carbowax" 600 was also present in the
formulation. Included in Table VII are
characterization data for these formulations and a
formulation containing only the "Carbowax" 600
additive.
. . .:
~L2~
28
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~ ~ o ~ o ~ o ~ o ~ o a o ~ o ~ o :~ o ~ o
P~ Z ~ Z ~ Z ~ Z ~ Z ~ Z ~ Z ~ Z P~ Z ~ Z
a:~ ~ o u~ a O
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28
- -` 127~
29
As shown by the ~ata in Table VII, the
additives of the present invention ("Tergitol"
15-S-3, 15-S-5 and 15-S-7) gave improved results (Ex.
8-10). "Tergitols" 15-S-9 to 40 (Ex. C-15 to 20)
gave significantly inferior drum deposit
performances. Moreover, the abrasion resistance
values observed became increasingly lower as the
number of ethylene oxide units in the "Tergitol"
additive was increased.
Example 11 and Cornparative Example 21
Fabric samples which have been prepared from
yarn sized with the size solution of the present
invention have been compared with fabric samples
identical in every respect except that the latter
were prepared with yarn sized with a commercial
PUA/tallow wax formulation. Both sets of samples
were desized under mild conditions (e.g. 15 seconds
soak at 55~C followed by three water rinses at
65C). The dye receptivity of the fabrics obtained
with the size of the present invention exhibited
! eight times the dye receptivity of those obtained
using the conventional wax-containing size. Moreover
dye absorption by the former was regular and uniform
whereas that exhibited by the latter was highly
irregular and nonuniform.
The fabric used in Examples 11 and 21
consisted of a 65/35 polyester/cotton warp having a
36 singles cotton count, and filled with a 100%
polyester weft so as to produce a ~2/83 construction
(ratio of warp threads to weft threads). The warp
yarn was sized with a size formulation containing
12.5% solids and contained a size add-on of 15.0%.
The size solution used in Example 11 corresponded
exactly to that used in Example 2. The size solution
used in Comparative Example 21 was the same as that
9~L4~
used in Comparative Example 2 except that it
contained 10%. "Synchem" llO wax instead of 8%.
