Note: Descriptions are shown in the official language in which they were submitted.
~ .1 76l2n
BA~KGROUND OF THE INVENTION
-
This invention relates to a method for permanently sizing
and, optionally, pigmenting a polyester or polyester-blend yarn.
The sizing of textile yarns prior to weaving is con-
ventional in the art. A principal object of sizing is to protect the
yarn from abrasion during the weaving operation and material such as
starches, polyvinyl alcohol, polyacrylates, polyacrylamides and poly-
esters are applied to the yarn and subsequently removed after the
weaving operation. Permanent sizes are also used to protect the yarn
during weaving, to stiffen the fabric and to bind a pigment or dye.
The present invention teaches a particularly suitable method for per-
manent size application employing a polymer latex formulation which
provides: a superior balance of polymer adhesion to polyester fibers,
fiber abrasion resistance under weaving conditions, wash and dry clean
durability of fabric produced from the fiber and, in many embodiments,
low foaming tendency of the formulation applied to the fiber.
Warp yarns, whether spun or filament, are composed of many
fine fibers which are soft and abrade easily. If left unprotected,
they could not withstand the rough mechanical action and abrasion they
are subjected to on a loom, whether shuttle or shuttleless. Therefore,
a size is applied to these yarns to protect them during the weaving
process, thus making fabric production possible. After the fabric is
woven, the size detracts from the textile aesthetics (hand or feel),
for most uses, and properties of the fabric (dyeability) so the size
is usually removed following weaving. ~owever, there are certain
textiles such as drapery, upholstery fabric, and mattress ticking, in
which the presence of a siz,e does not detract from the fabric but
actually enhances the desirable properties thereof.
The manufacture of such sized textiles may entail the
permanent sizing of polyester or polyester-blend yarn where the yarn
is not only sized in a normal slashing operation but permanently
colored simultaneously. This process protects the yarn for weaving
and eliminates the necessity of post-dyeing the yarn after it is
woven into fabric. This is especially useful when yarn dyed filling
(weft) is used to give a solid or multi-colored fabric. Also energy
*`
- 3 ~76121)
can be saved when easily dyeable filling yarns are used. The
principal required properties for such a size are:
Warp Size Requirements: (1) good bath stability,
(2) no foaming, (3) no building up on dry cans, (4) good leasing
properties, (5) minimal binder or color migration during drying,
(6) no tack in the warp beam, and (7) no shredding during weaving.
Pigment Dyeing Requirements: (1) binder must cure
in available heat (ca. 130 C.), (2) be durable to a peroxide
bleach process, (3) be durable to home laundering and dry cleaning,
(4) withstand spot cleaning without a loss in color, and (5)
produce maximum color yield.
Employing the pigmented size of the instant invention
represents considerable savings over prior art processes because
a process step, the post-dyeing of the fabric or yarn, is eliminated.
With polyester yarns, the dye step normally requires both high
temperature and pressure each of which represents a considerable
use of energy. Another energy consuming step, the desizing of
the fabric normally done in a hot bath, is also eliminated.
Partial savings are realized when a warp yarn is pre-dyed, by
the process of this invention, and used with an undyed fill yarn
which is more easily dyed, such as cotton or rayon, and thus may
be dyed by a mild and less energy demanding process. A particular
example would be a drapery which uses a polyester warp and a
viscose fill.
This pigmented sizing produces materials with as
good or better color fastness than dyed yarn. Elimination of
the desizing step means that the many advantages are carried
over into the final fabric. Altogether the process of this
invention thus makes available an inexpensive, color fast, con-
venient, high quality, pigment dyed yarn at a considerable reduc-
tion in the use of energy, labor, equipment and chemical raw
materials. Pigments are generally cheaper than dyes but hereto-
fore high quality color fastness via pigment has been difficult.
The process of this invention achieves good fastness as well as
high color yield thus representing a further saving. Dyes,
especially for polyester, require auxiliaries such as defoamers,
leveling agents, solvents, and carriers in addition to the dye
itself as well as a size which then must be removed before
~ 17612~
--3--
the dyeing step. Thus the process of the instant invention
inherently entails the ecological improvements of requiring 1
no solvent or carrier, 2) no disposal of the removed size, 3)
less dissipated heat, 4) less water usage and 5) less waste
water disposal. The yarn produced by the process of the instant
invention yields, by ar~-known weaving processes, a fabric which
has a firm hand, is abrasion resistant, strong and peroxide
bleach resistant (particularly required if any direct dyes are
present) as well as being laundry and dry clean resistant. The
yarn size of this invention gives better adhesion to the, chemi-
cally similar, acrylic back coatings widely used with drapery,mattress ticking and upholstery fabrics. The improved strength,
abrasion resistance and adhesion all work together to increase
the fabric life.
BRIEF DESCRIPTION OF INVENTION
In accordance with the present invention there is
provided a method for permanently sizing and optionally pig-
menting polyester filaments and yarns or blends of polyester
with other fibrous or filament ma~erials which blends are prefer-
ably at least 50% polyester. The method entails applying to the
yarn a polymer latex, a melamine aminoplast resin, and, optionally,
a pigment and subsequently curing the treated yarn. The latex
polymer is of monomers comprising, by weight, 45 to 65% of one
or more of a C4 to C8 alkyl acrylate, 28 to 52% of one or more
of a vinyl aromatic monomer or a mixture thereof with up to an
equal weight of methyl methacrylate, and 3 to 14% of acrylic
acid, methacrylic acid, itaconic acid or a mixture thereof.
DETAILED DESCRIPTION
There is provided in the present invention a method
for permanently sizing and optionally pigmenting polyester and
polyester-blend yarns by applying thereto a formulation com-
prising a polymer latex and a melamine aminoplast resin,
suitable for crosslinking the latex polymer, and, optionally, a
pigment, and subsequently drying and curing the treated yarn.
~ ~7612~
--4--
The polymer latex of the instant invention prefer-
ably is made by a gradual addition thermal emulsion polymerization
process to yield the product at about 35 to 50% solids. Such
processes are taught in books entitled "Emulsion Polymerization"
by D. C. Blackley (Wiley, 1975) and S. A. Bovey et al (Inter-
science Publishers, 1965). The polymer is preferably a linear
polymer free of crosslinks and branch points. The polymer is
prepared from monomers comprising, by weight, 4S to 65~,
preferably 50 to 59% of a C4 to C8 alkyl acrylate or a mixture
thereof, preferably n-butyl acrylate; 28 to 52~, preferably 31
to 46%, of a vinyl aromatic monomer such as styrene, alpha-methyl
styrene, and vinyl toluene, or a mixture thereof preferably
styrene, with the further proviso that up to half of the vinyl
aromatic monomer may be replaced by methyl methacrylate; and
3-14%, preferably 4-12% acrylic acid, methacrylic acid and, less
preferably, itaconic acid or a mixture of these. Most preferably
the monomers consist essentially of 50 to 59% butyl acrylate, 31
to 46% styrene and 4 to 12% acrylic acid or methacrylic acid.
Desirably, the latex polymer has a weight average molecular
weight of about 0.3 to about 2.5 million with 0.5 to about 2.0
million being preferred and 0.6 to 1.5 million being most preferred.
- The diameter of the latex particles is usually between
0.05 and 0.5 microns with the range 0.1 to 0.2 microns being
preferred.
The stiffness of the latex polymer is a particularly
significant property. If the polymer is too stiff the size will
be too hard and will flake off of the yarn as the yarn is flexed
during weaving. If the polymer is too soft it will be too sticky
causing friction in the loom, sticking to the reeds, and easy
removal from the yarn by abrasion, and these processes may further
cause a build up of the polymer on parts of the machines employed
in processing the yarns and making fabric. Because of these
property limitations it is preferred that the latex polymer have
I ~7612(1
a T300 between 0 C. and 40 C. with the range 10 C. to 30 C.
being more preferred. T300 is the temperature at which the ten
secor.d, torsional modulus of a film, made by drying the polymer
latex, is 300 kilograms per square centimeter as measured by the
American Society For Testing And Materlals standard method of test
D 1043-72. As 300 kgs. per sq. cm. is roughly twenty fold below
the glassy modulus of amorphous polymers, such as those of interest
herein, the T300 is appreciably higher than the ylass transition
temperature (Tg); the difference is usually about 15 C. which
value may be used to obtain estimates of T300 from tables of Tg
data or calculations (see Fox, Bull. Am. Physics Soc. 1, 3 page
123 (1956) and "Polymer Handbook" 2nd ed, Brandrup and Immergut
eds, (John Wiley, N.Y. 1975) Section III, part 2 by Lee and
R~therford).
The melamine aminoplast condensates which are employed
are either low molecular weight oligomeric or monomeric reaction
products of formaldehyde and melamine such as N,N-dimethylolmelamine
and alcohol-modified melamine formaldehyde thermosetting resin
condensates, e.g. methyl and ethyl alcohol modified, for example,
dimethoxymethyl monomethylolmelamine, etc. Preferably, the extent
of condensation of these resin-forming aminoplast condensates is
such that they are still soluble in water or self-dispersible
therein to a colloidal condition. The melamine aminoplast is
present at 2 to 40%, preferably 4 to 25% and most preferably 8 to
15% by weight of the latex copolymer. The preferred aminoplasts
~5 are hexamethoxymethyl melamine, such as CymelR 303, and partially
methylated polymeric melamine having an equivalent weight about
225 to about 325, such as Cymel 373. Other useful melamine amino-
plasts are sold under the tradename AerotexR including Aerotex M-
3, Aerotex 900 and Aerotex 23SP.
The amount of copolymer applied to the yarn material
may vary from about 0.5 to about 20% by weight depending on the
purpose for which the application is intended and on whether or
not auxiliary conditioning or sizing agents are included in the
composition when it is applied to the yarn. The aqueous bath
I l7612~
formulation comprising the copolymer latex may be applied by
spraying, dipping, padding, by sizing rolls, transfer rolls or
the like, dipping being preferred. An entire warp may be passed
through a conventional slasher or a yarn may be individually
treated in a single end sizer. The latex has a concentration of
1-25~ by weight solids in the application formulation and excess
is removed, such as by squeeze rolls or wipers, and the treated
yarn is then dried. Drying is effected by any suitable means
such as by heated air or drying cans. Drying may be effected at
a wide range of temperatures, such as from 70-120 C, or in
conjunction with curing. The formulation is applied at room
temperature or at elevated temperatures such as up to about ~0
C. For warp sizing of spun yarns the preferred proportion of
polymer applied to the yarn is from 5-15% by weight of the initial
weight of the yarn. For the sizing of continuous filament yarns,
the preferred proportion is from about 1% to about 10~ copolymer
on the weight of the yarn. The higher amount of size is often
needed for fine (low) denier zero or low twist yarn. The preferred
size add-on for 150 denier zero twist polyester filament is 2.5
- 3.0% (copolymer on yarn).
The article obtained, after application of the sizing
composition to the yarn and drying, is essentially free from the
disadvantage of developing static charges and loss of sizing
material by transfer to guides or by shedding.
The permanent size of the instant application is
applied to a yarn which is a polyester, preferably polyethylene
terephthalate, yarn or alternatively a polyester-blend yarn.
Filament yarn substrates are preferred although spun yarns are
useful. Blend yarns include blends of polyester with up to 50
of other, préferably organic, fibers including natural fibers,
such as cotton, and synthetic fibers, such as rayon; the cotton
blend being preferred.
! ~76121~
7_
The formulation for application of the polymer to
the yarn preferably contains a rheology modifier, such as a
homopolymer or a copolymer of an ethylenically-unsaturated acid,
such as polyacrylic acid, polymethacrylic acid and hydrolyzed
styrene/maleic anhydride copolymer; other carboxyl polymers such
S as carboxymethyl cellulose; water-soluble or water-
dispersible non-ionic polymers/ such as hydroxyethyl cellulose,
polyoxyethylene polymers (although the latter polymers are not
as efficient as the ionic polymers), and homo- and co-
polymers of acrylamide. Volatile bases, such as ammonia and
amines, are used for partial or complete neutralization of the
rheology modifiers.
For immersion treatment of the yarn a desirable
formulation has, on a solids basis, 3 to 15%, preferably 4 to 8
latex polymer; 0 to 12~, preferably 0 to 8%, most preferably 0
to 4% pigment; 0.05 to 6%, preferably 0.3 to 3% melamine amino-
plast, 0.1 to 2.0%, preferably 0.3 to 1.0%, rheology
modifier or thickener, and up to 0.6~, preferably up to 0.3~
catalyst for the melamine resin; in many embodiments of this
invention no such catalyst is preferred. Optionally, surfactants,
anti-foam agents, penetrants, alkaline materials to control the
pH tpreferably volatile amines and most preferably ammonia),
penetrants and other additives known to those skilled in the art
are used to achieve specific desirable properties in the formula-
tion or the yarn.
Anionic surfactants which may be added to the formula-
tion include the following: sulfosuccinates, such as sodium
bis(2-ethylhexyl)sulfosuccinate; sulfates, such as sodium lauryl
sulfate; sulfonates, such as sodium isopropylnaphthalene sulfo-
nate; alkyl aryl polyester sulfates and sulfonates, phosphate
ester types and the like.
Nonionic surfactants which may be added to the formula-
tion include the following: octylphenoxypoly(ethyleneoxy)ethanol,
trimethylnonyloxypoly(ethyleneoxy)ethanol, nonylphenoxypoly
(ethyleneoxy)ethanol, glyceryl trioleate, ethyleneglycol
ethyleneglycol monostearate, sorbitan trioleate, sorbitan tri-
stearate, and the like.
I ~7612~
--8--
Nonionic and anionic penetrating agents and antifoaming agents
commonly used by those skilled in the art of sizing and coloring
may also be employed. Suitable penetrating agents which may be
used include the following: diethanolamine, N-aminoethyl ethanol-
amine, ethylene glycol monobutyl ether, diethylene glycol, diethyl-
ene glycol monobutyl ether, dipropylene glycol monomethyl ether,ethylene glycol, dihexyl sodium sulfosuccinate, and the like.
Suitable antifoaming agents which may be used include the following
isobutanol, n-butanol, iso-decanol, dibutyl phthalate, diethylene
glycol laurate, 2-ethylhexanol, n-octanol, polypropylene glycol,
tributyl citrate, and the like.
The curing catalysts ~or the aminoplast which may be used
include amine or ammonium salts such as ammonium chloride, ammonium
nitrate~ ammonium sulfate, ammonium acid phosphate, isopropanolamine
hydrochloride, and the like. Generally, any such catalyst may be
used with about equal results as may other latent acid catalysts
including Lewis acid catalysts.
Any pigments commonly used in textile pigmentation are
usable. Suitable water-immiscible colorants which may be used
include the following wherein C. I. means Colour Index (published
by The Society of Dyers and Colourists): C. I. Direct Blue 86, C.
I. Pigment Yellow 14, C. I. Pigment Blue 15, C. I. Pigment Black
7, C. I. Pigment Green 1, C. I. Pigment Orange 5, C. I. Pigment
Red 12, and the like. The preferred colorants are C. I. Pigment
Blue 15, and Yellow QR.
The application of the sizing, or colorant-binding,
composition to the yarn is by the methods described above, to
deposit thereon about 1-10~, preferably 2-5%, by weight solids
from the aforedescribed latex polymer formulation. The preferred
substrate material is a polyester filament warp yarn.
The treated yarn is dried and cured by heating at 100-350
F. for a period of about 5 seconds to 5 minutes, preferably at
250-320 F. for a period of about 15 seconds to 2 minutes.
~ .~76l2n
- 9 -
1 Optionally the treated yarn may be dried at a lower temperature,
such as by standing at room temperature until dry, and then cured
at 225-320 F. for a period o~ about 10 seconds to 2 minutes,
preferably at 225-300 F. for a period of about 15 seconds to 1
minute.
The process of this invention produces an insoluble size or
colorant-binding coating on the yarn substrate which is durable to
laundering and dry cleaning. The treated substrate has
satisfactory handle and is tack-free. The treated polyester warp
yarn is characterized by excellent weaving characteristics.
In the following examples, which are illustrative of the
invention, the parts and percentages are by weight and the
temperatures are in degrees Celsius unless otherwise expressly
noted. The following abbreviations are used.
SLS sodium lauryl sulfate
ME monomer emulsion
APS ammonium persulfate
AA acrylic acid
St styrene
BA n-butyl acrylate
OPE 9.7 octylphenoxypoly(8.7)ethoxy ethanol
S/S solids on solids
T-300 temperature at which the 10 second
torsional modulus is 300 kg/cm2
Tg glass transition temperature
MAA methacrylic acid
MHI methyl hydrogen itaconate
HEMA hydroxyethyl methacrylate
EA ethyl acrylate
EHA 2-ethylhexyl acrylate
IBA isobutyl acrylate
MD machine direction
MMA methyl methacrylate
Example A - Preparation of Emulsion Polymer at 4% Acid
The preparation is a gradual addition thermal process
producing a latex polymer 58.5% BA, 37.5% St and 4~ AA.
-lo- l l7612~
Ingredients
Kettle Charges Monomer Emulsion (ME)
885 g. Water 987 g. Water
1.8 g. SLS (28~) 16.1 g. SLS (28~)
100 g. ME 80 g. AA
( 4.0 g.~ APS in 650 g. St
25_ g.) Water 1270 g. BA
915.8 g. (without ME) 3003.1 g.
Cofeed
4.0 g. APS
120 g. Water
124 g.
Process
Water and SLS are charged to a 5-liter kettle and heated
to 82 C. The monomer preform, a 100 g. portion of the monomer
emulsion, is added, followed by the APS in water, initiator solution.
Ten minutes later, gradual addition of the monomer emulsion, to
which had been added the co-feed solution, is begun at 82 C.
and continued at a constant rate for 2 hours, while the temperature
is held at 82 - 86 C. A 15-minute hold at that temperature
follows the end of the gradual addition, then the reaction mixture
is cooled to 55 C. Residual monomers are removed by free radical
chasers. The batch is then cooled to room temperature and filtered
through cheesecloth.
Properties
% Solids = 46.1
% conversion = 99.1
Viscosity avg. molec. wt. = 700,000
pH = 2.1
Viscosity = 32 cps. (Brookfield Viscometer,
spindle #1,60 rpm)
I l7612~
1 The pH may be elevated by the addition of aqueous ammonia
to about 4.5, as was done in the case of the material used in
formulations I, V, and IX, Table I, or higher such as 6, for
convenience, long term stability, etc.
Example B - Preparation of Emulsion Polymer at 12% Acid
The preparation is a gradual addition thermal process
producing a latex polymer, 57% BA, 31% St, and 12~ MAA.
Ingredients
Kettle Charges Monomer Emulsion (ME)
976 g. Water 968 g. Water
2.6 g. SLS (28%) 18.7 g. SLS (28%)
114 g. ME 191 g. ~AA
4.0 g.~ APS in 473 g. St
~ 25 g. ~ Water 906 g. BA
Cofeed
4.0 g. APS
205 g. Water
Process
Water and SLS are charged to a 5-liter kettle and heated
to 84C. The monomer preform, a 114 g. portion of the monomer
emulsion, is added, followed by the APS in water kettle charged
initiator solution. Ten minutes later, gradual addition of
the monomer emulsion at 20 g./min. and of the cofeed catalyst
at 1.7 g./min. is begun and continued at a constant rate
while the temperature is held at 83 to 85C. A 15 minute
hold at the final temperature is maintained and then the
reaction mixture is cooled to 55C. Residual monomers are
removed by means of free radical chasers. The batch is then
cooled to room temperature and filtered through cheesecloth~
Properties
% solids = 38.7
pH = 2.6
Viscosity = 7.0 cps. (grookfield Viscometer,
spindle #1, 60 rpm)
~ ~7612~t
-12-
Example C - A Harder 4~ Acid Emulsion Polymer
Employing the preparation method of Example A, a co-
polymer having the composition 50 BA/46 St/4 AA is prepared
at 45% total solids and a pH of 4.5.
S Example D - A Harder 12~ ACid Emulsion Polymer
Employing the preparation method of Example B, a polymer
emulsion is made having the composition 50.5 BA/37 St/12 AA
at a total solids of 39.5% and pH of 2.3.
Preparation of Formulations
A control formulation for the pigment sizing of polyester
warp yarns is based on a commercial water dispersible polyester
used as a size (Eastman WD), a melamine formaldehyde resin
for crosslinking (Cymel 373), a latent acid catalyst, Acrysol
G-llO as rheology modifier and anti-migrant, and a pigment.
The formulation follows:
Water 72.8
Eastman3 WD (30% in water) 20.0 polymer size
Acrysol~ G-1104(50% in water) 5.0 rheology modifier,
(Rohm and Haas Co.) antimigrant
Cymel~ 3731(American Cyan- 1.0 crosslinker
amide Co.)
Ammonium Nitrate(25~ in water)0.2 catalyst
Pigment2 dispersion 1.0 Colorant
Total 100.0
Brookfield Viscosity Model
LVT, #1 spindle at 60 rpm 1~ cps
% Size polymer Solids 6%
(Eastman WD)
Notes:
30 lCymel 373 - partially methylated polymeric melamine;
equivalent wt. 225 to 325.
2Pigment- American Hoechst - Yellow QR
3Eastman WD - water dispersible polyester size
4Acrysol G-llO- ammonium polyacrylate solution; viscosity 5
aqueous is 90 to 170 cps.
~ ,1 76l2n
1 The above formulation is compared to the following
systems based on the Examples A-D copolymers ~Table I). A
water insoluble melamine formaldehyde resin, Cymel 303, is
employed at two levels, 0.3 and 1.0%, the second is e~uivalent
to the Cymel 373 level used in these formulations and with Eastman
WD. Following the first three formulations the latent acid
catalyst is removed from the for~.ulation since the desired
performance is achieved without a catalyst.
~ .l76l2n
- 1 4 -
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I 17612(1
-15-
1 Preparation of Yarn
Each formulation is applied to polyester filament yarn
(Avitex Fibers, Inc. Type 200-F polyester 150 denier, 50 filament,
0 twist) on a laboratory single end slasher run at 4M/min. The
yarns are either dried thru a dry tube (a 1 meter heated glass
tube) for 15 seconds at 115 C. and post cured in a forced air
oven for 45 seconds at 132 C. (Example 1) or dried and cured
in the dry tube set at 132 C. for 15 seconds (Example 2). The
amount of polymer applied to the yarn is believed .o be 3 to 5% of
the weight of the yarn.
All sized yarn is conditioned one day at 21 C. and 60%
RH before testing.
Preparation of Fil~s
Thin films are cast on a 2 mil Mylar~ film with a
#30 wire wound rod, dried for 3 minutes at 115 C. and cured for
45 seconds at 132 C. in a forced air oven.
Evaluation of Results - See Table 2
Adhesion: The sized yarns are evaluated for adhesion
using a laboratory sand tumble test (as follows):
Sand Tumble Test: Duplicate 3 yd. skeins of sized
yarn are placed in an 8 oz. jar containing 150 g.
of course sand, rotated for 30 minutes on an Atlas
Launder-ometer~, removed and rated for percent
of the fiber bundle remaining intact; the sand
rating (STR).
In a second "adhesion to polyester" test the
adhesion to Mylar (thin film) of each formulation
is determined by a crinkle test. The test is
designed to measure film adhesion to polyester
sheet by crumbling the sheet by hand and
flattening it noting film separation or cracking.
All the formulations including the control ha~e
excellent adhesion. No cracks or separation are
noted. Tack is also rated and none of the films are
tacky.
~ .17612n
-16-
1 Durabilit tG a Peroxide Bleach Process
Y
Each formulation is tested for durability to a
rather stringent process solution. Thirty yard
skeins of the sized yarns are subjected to bleaching
in the bleach process solution with mild agitation at the
stated time and temperature conditions. The
yarn is then compared to unbleached yarn for changes in
color, feel and filament to filament adhesion and for the
amount of color in the bleach .solution.
Bleach Process Solution
1% H22 - 50% Active
0.1% Sodium Silicate
0.05% NaOH - 50% Active
0.05% Detergent Triton~ X-305 Rohm and Iic~s Co~
Run for 1 hour at 93 C. Ri~se in hot water.
The results are recorded as follows:
Yarn Conditions -
Excellent = no loss in color or feel
Good = slight loss in feel
Fair = separation of yarn filaments
Poor = major loss in color and
separation of yarn filaments
Bleach Solution - ~ellow, pale yellow, pale tinge,
clear in improving order.
_olvent Resistance
Two solvent resistance tests are run - one relating
to dry cleaning, the other to spot cleaning. The dry
cleaning test consists of soaking pieces of the thin
film, cast on Mylar, in perchloroethylene for 30
minutes and evaluating changes. In each case, the wet
films are "grabby" and show a slight reduction in
adhesion, however, when dried there are no differences
between the soaked and control films. There is no
color bleeding into the perchloroethylene.
~ .1 76l2n
1 The resistance to spot cleaning is tested by
mounting small skeins of yarn on white cardboard and
spraying them with 1,1,1 trichloroethane noting color
loss or color running. This test is done on yarn
dried and cured simultaneously (Example 2) and in all
cases there is no loss in color or running of the
pigment. Therefore, all are considered to have
excellent spot clean resistance and good durability
to dry cleaning.
Formulation Stability
Each formulation is monitored for stability
(settling or coagulation).
~ 17612t!
--18--
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-20-
Example 3 - Polymer Substantivity to Polyester
Other emulsion polymers are tested for substantivity
to a polyester substrate by determining the tensile strength
of a water wet non-woven polyester fabric employing the polymer
as its binder. High strength indicates good substantivity of
the polymer composition to the polyester or polyester-blend and
thus is indicative of good performance, when formulated, cross-
linked and cured, as a permanent size.
Polymer emulsions ~Example E through O), prepared by the
general procedure of Example A, are formulated to 6% binder solids.
A typical formulation is:
Water - 521.1 g.
25% OPE 9.7 - 0.7 g.
Polymer emulsion (46~ -78.9 g.
solids)
The pH of the mix may be adjusted with ammonia as desired
without significantly effecting web properties, in these examples
it is between 2 and 9.
Carded polyester web (0.5 oz./yd., 17.2 g./m.2) is prepared
using Dacron ~ type 54W (Merge 113505) (DuPont) fiber of 1.5
denier and 1.5 in., 3.8 cm., staple length. The webs are
supported between two layers of fiberglass scrim and saturated
by 6% polymer solids baths on a Birch Brothers Padder at 40 lbs.,
18 kg nip roll pressure with a speed of 7.6 yds./min.,
6.9 m./min. The padded webs are dried for 7 minutes at 65 C.
in a forced air oven. To insure that all samples receive a
similar heat treatment, all webs are cured for 1.5 minutes at
150 C. except when otherwise noted. The finished fabrics weigh
0.7 oz./yd.2, 24 g./m.2, and contain 30% binder.
Fabrics are tested for wet tensile strength after soaking
for 30 minutes in room temperature water and blotting lightly
with a towel after removal from the water bath. Specimens are
cut to 1" x 6.5" (2.5 cm x 16.5 cm) in the machine direction
and are tested on an Instron~ tester with a jaw separation of
5" (12.7 cm) and an extension rate of 2" (5.1 cm)/minute in the
machine direction.
I .t76l2n
All compositions contain 4~ acrylic acid monomer as does
Example A which is used as an internal control for the series.
Properties of polymers yielding fabrics ~ith a water-wet
tensile strength similar to that of a fabric of Example A produce
sized yarns having the acceptable adhesion, durability to bleach,
solvent resistance and stability,characterized by the polymer of
Example A,when formulated and applied as a permanent size to a
polyester or a polyester-blend yarn.
Water Wet Tensile
Binder Composition Strength, Kg
Example E 96 BA/4 AA 0.3
" F 85 BA/ll St/4 AA 0.8
" G 75 BA/21 St/4 AA 2.3
" H 70 BA/26 St/4 AA 2.6
" I(l) 63.5 BA/32.5 St/4 AA 2.3
A(2) 58.5 BA/37.5 St/4 AA 2.3
" J 40 BA/56 St/4 AA l.l
" K 30 BA/66 St/4 AA 0.6
" L 63.5 EHA/32.5 St/4 AA 3.0
n M 63.5 IBA/32.5 St/4 AA 2.8
" N 63.5 BA/16.25 St/16.25 2.0
MMA/4 AA
" O 53.5 BA/10 EA/32.5 St/4 AA l.9
(1) Viscosity average molecular weight 950,000
(2) Viscosity average molecular weight 700,000
Inspection of these data shows a number of interesting
things. There is a marked drop-off in substantivity when the
polymer contains more than 75% butyl acrylate mer units and,
at the other end of the range, when the butyl acrylate mer units
are as low as 40% of the polymer. Substitution of methyl meth-
acrylate for half of the styrene in the copolymer produces
a small decrease in the water-wet tensile strength of the
fabric. Replacement of a limited amount of butyl acrylate
by ethyl acrylate has a similar effect.
- ~
~ 17612(1
22-
When binder A is used to bond a rayon/polyester
(1/1) non-woven fabric a water-wet tensile strength of 1.6
kgs. is obtained, thus the polymer is effective on this sub-
strate as well. The rayon/polyester fabric is made from
DuPont Dacron~ type 54 W (1.5 denier/4.0 cm.) polyester and
FMC viscose rayon (1.5 denier-4.0 cm.). The finished fabric
weighs 23.7 g. per sq. meter and contains 30% binder on fabric
weight. Polyester-rayon yarns permanently sized with Example A
po~ymer, using the procedures and formulations of experiments
1 and 2,are acceptable sized yarns.
