Acrylic Resins in Textile

Processing
A. C. NUESSLE AND B. B. KINE e
Research Laboratories, Rohm & Haas Co., Philadelphia, Pa.

NTIL a few decades ago, the only polymeric materials em- ties responsible for their utility in certain applications. Other
Q
ployed in the finishing of textiles were naturally occurring polymer types are mentioned where it is desirable to show simi-
substances such as rosin, gelatin, and various starches and gums. larities or differences, because the use of acrylics in a particular
Today, however, the industry utilizes a large variety of synthetic application will be unique only where other polymers do not have
polymers to achieve effects not possible with the natural products. the required properties.
One group of synthetics which enjoys such use is the acrylics
1
family, composed of resins derived from acrylic acid and related GENERAL PHYSICOCHEMICAL CONSIDERATIONS
compounds. A simplified picture of the chemical relationship
A linear polymer may exist in any one of three states, depend-
between the acrylics and other synthetic polymers commonly
ing on its temperature, its chemical nature, and its molecular
utilized in textile finishing is shown:
weight. Below a certain temperature the polymer is frozen in a
glassy state, in which it possesses the mechanical properties of a
Synthetic Polymers rigid solid. With increasing temperature there occurs a second-

Condensation
I Addition
order transition, beyond which
the polymer enters a plastic state
wherein under small periods of
polymers polymers applied stress it has the revers-

I
Formaldehyde Polyesters
I'
sym-Ethylenes unsym-Ethylenes
ible deformation of a rubber.
At a still higher temperature
the polymer may enter a state of
viscous flow, in which nonrevers-

7-
condensates
ible deformations take place;

I
Nitrogenous Nonnitrogenous
this occurs most readily with
polymers of low molecular
weight, but may also occur with
I
Urea F
I
Phenol F Maleic derivatives Vinyl esters
high polymers if the temperature
is sufficiently elevated. Under
Melamine F Ketone F (generally Vinylidene normal conditions of use, how-
copolymers) halides ever, most linear polymers em-
Styrene
Acrvlics ployed in the textile industry
are in either the glassy or the
rubbery state.
The acrylics are a sdbdivision of the unsymmetrically sub- The transition from glassy t o rubbery is a fairly sharp one,
stituted ethylene class, which comprises a large number of resins but the observed value of the transition temperature may vary
obtained by the polymerization of monomers containing a widely, depending on the method of test; probably the most
CHz=C< group. It is not unexpected, therefore, that in proper- critical variable is the rate of testing. A number of mechanical
tests have been proposed, involving softening temperature (1),
ties and uses they are more closely related to vinyl polymers such
brittle point (9),Young's modulus (9), and the like. A typical
as polystyrene or polyvinyl acetate, than to the condensation
curve, showing the effect of temperature on torsional stiffness,
resins such as the urea-formaldehydes. is given in Figure 1.
The acrylic monomers include both acrylic and methacrylic
A comparison of test methods is outside the scope of this paper.
acids, and their salts, esters, amides, and nitriles:
Of greater importance to the present discussion is the fact that,
under specific conditions of test, the location of Tg varies markedly
CHz=CH CH-CH CH-CH CHFCH
2- I I with the chemical composition of the polymer. For example,
bOOH COONa COOR CONHz an ethyl acrylate polymer may have a transition temperature of
-20' C., while a polymer of ethyl methacrylate may have a Tg
Acrylic Acrylate Acrylic Acrylamide of f55" C., as indicated in Figure 2. At room temperature the
acid salt ester
ethyl polyacrylate would be soft and rubbery, while the ethyl
polymethacrylate would be stiff. The stiffness of a polymer in

CHz=CH
I CHa=l
8"" etc.
the rubbery state also tends to increase with molecular weight,
but most polymers used in textile applications are polymerized
to a degree where the effect of molecular size is no longer critical.
CN COOH
Accordingly, the transition temperatures of the various polymers,
Acrylonitrile Methacrylic and their relative stiffness a t a given temperature, are determined
acid primarily by their chemical constitution.
The following generalizations may be made concerning the
The present paper is concerned with textile uses of acrylics, relationship between chemical structure and physical properties
and especially with some of the chemical and physical proper- of the acrylic polymers.
1287
1288 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 45, No, 6

tion in ethylene dichloride or other suitable solvent. Because of

greater fire hazard, toxicity, and expense, this is usually less de-
sirable than an application from water medium, but finds use in
applications where a very glossy surface coating is desired.
FROMEMULSION POLYMER. The water-insoluble monomers
may be polymerized in emulsion form, to produce an aqueouq
dispersion or latex. Properly made, such dispersions are stable
in storage for a year or more, and may be readily diluted with
water to any degree a t time of use. On drying, most dispersions
are irreversibly broken, so that the finish is wash-fast. Because
t
60 GLASSY
of the ease of application, this is the most popular method of
applying the water-insoluble acrylics to textiles.
APPLIEDAS MONOMER.There are many ways of applying an
acrylic monomer (or combination of monomers) to a textile
material, and subsequently bringing about polymerization in
place. By such means, the polymer can in many instances be
built up within the fiber, rather than deposited on the surface.
Some attention has been given to this method by various in-
vestigators, although thus far little commercial utilization has
resulted.
It is evident that the acrylics are most often applied either from
water solution or from aqueous emulsion.

EMCLSIOM POLYMERS

Tg TEMPERATURE -
F i g u r e 1. Effect of Temperature on Torsional
PHYSICAL PROPERTIES AXD ESD USE. One of the most com-
mon objectives of textile finishing is the modification of the
“hand” or feel of a fabric. By this means it is possible to weave a
standard fabri: and modify it later to meet the requirements of
Stiffness
the current fashion trend. It is also possible to take a light,
inexpensive fabric and build it up to simulate a heavier, more
expensive fabric. This is generally done by treating the fabric
Because the alkyl group tends to separate the polymer mole-
cules and act as a plasticizer, the lower members of the n-alkyl with a polymeric material which will penetrate the yarns and
acrylate series become even softer with increasing length of the bind the fibers together, and also bond the yarns a t the crossover
alkyl chain. Higher in the series, there is a reversal as a waxy points. Thus the fabric becomes less multifilamentous, and
stiffness sets in owing to the tendency of the longer alkyl chains
to crystallize. Brittle point measurements, which determine

11
the temperature a t which an arbitrary brittle stiffness is attained,
set the minimum a t n-octyl(9); however, a test based on relative
hardness a t a fixed, more elevated temperature-e.g., room tem-
perature-would put the minimum somewhat higher.
The n-alkyl methacrylates similarly become softer, to a mini-
tI
mum, by brittle point, a t dodecyl ( 8 ) .
Branched-chain alkyl esters have greater rigidity than the
corresponding straight-chain esters. The tert-butyl esters are
especially stiff ( 7 ) .
Acrylonitrile and methacrylonitrile polymers are very stiff EA
and have a very high Tg,presumably because of strong hydro-
gen-bonding tendencies of the compact, polar nitrile group.
The polyacids, their amides, and their alkali salts, which are
so strongly polar as to be generally water-soluble, give stiff films
having relatively little thermoplasticity.
The effect of copolymerization tends to be additive, with the
copolymer exhibiting physical properties intermediate between
those of its components. Thus, the physical as well as chemical
- 20
-
properties can be varied over a wide range by suitable choice of ROOM TEMP +55
monomer combinations.
PEkrbiYk “6.
One other important factor which may influence the physical Figure 2. Effect of Chemical Composition on
properties of a polymer film is its mode of preparation. A film Transition Temperature
laid down from emulsion-Le., latex-may be somewhat less
continuous than one laid down from solvent, particularly if the
transition temperature is high. As is illustrated in a later sec- therefore less flexible. I n order to do this, the polymer must
tion, this can influence the type of finish obtained on the textile adhere t o the fibers; but assuming good adhesion (as is almost
fabric. invariably the case with cellulosic fabrics) the effect on fabric
Lfhand”is then dependent to a large degree on the physical proper-
METHOD OF APPLICATION ties of the polymer.
There are four general methods of applying acrylics to textile For example, consider the effect of two conlmercially available
materials: acrylic dispersions applied to an 80 x 80 cotton sheeting. One
of these, designated as emulsion A, when dried doivn on gla%
FROM WATERSOLUTION.The water-soluble polymers include in the absence of fabric, yields a soft, rubbery film, whereas the
polyacrylic and polymethacrylic acids, their alkali and am- other, emulsion R,dries to a hard film. Each of these products
monium salts, and their amides. Acrylonitrile and the acrylic was padded onto the fabric a t two concentrations and dried a t
esters cannot be so applied, unless copolymerized with a sub- two temperatures. Stiffness tests were then made using the
stantial proportion of one of the water-soluble acrylics. Applied Gurley tester (9) which measures the force required to bend the
to textile yarns or fabrics, such materials usually remain mater- fabric sample unilaterally. Although m r h a test cannot take into
soluble, unless insolubilized by some special method, and are account all of the many factors Tvhich go to make up the complex
therefore most useful where wash-fastness is not required. property known as hand, it does give an objective meawrement
FROM SOLVENT SOLUTION. The acrylic esters and their co- of one important fabric property-flexural stiffness. The data
polymers with acrylonitrile may generally be applied from solu- are listed in Table I .
 June 1953 INDUSTRIAL AND ENGINEERING CHEMISTRY 1289
It is apparent that stiffness increases with concentration (as The necessity of fusing the dispersed particles to obtain proper
would be expected), and also increases slightly with tempera- cohesion is shown in the effect of drying temperature on copoly-
ture of drying (because of more com lete fusion of the emulsion mer EM. Drying at 150' C. almost doubled the stiffness over
particles). Far greater, however, is t%e difference between prod-
ucts: Emulsion B, which dries to a hard film, imparts consider- that obtained a t room temperature.
able stiffness t o the-fabric, while emulsion A, which dries to a Each of these polymers, if precipitated from the dispersion
soft, rubbery film, Gves little stiffness b u t imparts full, heavy and dissolved in a suitable solvent, will then dry down to a con-
feel, which unfortunately cannot easily be reduced to a single
numerical quantity. As these materials are both acrylics, it is tinuous film, as there are no longer any discrete particles which
obvious that a range of effects is available, depending on the need to be fused. The molecular flow required for film formation
type of acrylic selected. is maintained during drying by residual solvent, which temporar-
ily lowers the transition temperature. Accordingly, polymer M
would be expected to give a stiff finish to fabric if applied from
TABLEI. FILMFORM
OF EMULSION
POLYMER
vs. EFFECTON
FABRIC solvent. Data in Table I11 show that this is so. It is also ap-
Drying Gurley parent that the drying temperature is much less critical when
Solids Tfmp., Stiffnessa, Hand of applying from solvent than when applying from aqueous dis-
Polymer Film Form on Fabric, C. Mg../In. Fabric
% persion.
Water control ...... ....
.. 120 6.6 Soft
150 6.6
A Soft, rubbery 3.9 120 10.2 TABLE
111. EFFECTOF SOLVENT
APPLICATIONS
3.9 150 10.4 Full, heavy
,. 7.7 120 12.0 Drying GurIey
7.7 150 13.2 T:mp., Stiffness, Hand of
B Hard, stiff 4.1 120 38 Stiff Solvent Solutions Film Form C. Mg./Inch Fabric
4 1
7.7
150
120
44
59
Solvent only ....... 25 7.2 Soft
150 7.1
7.7 150 62 E (EA) Soft, rubbery 25 12 Full, heavy
a Test made in warp direction. 150 11
E M (EA/MMA) Stiff, flexible 25 65 Stiff
150 73
M (MMA) Very stiff, brittle 25 112 Very stiff
150 111
To illustrate further the variety of effects, and t o show how a About 4% solids in ethylene dichloride.
monomer composition controls the physical properties of the
film and therefore the type of finish obtained, the following series
of polymers was studied:
Another way in which a dispersion of a hard polymer such as
E 100% ethyl acrylate M may be made to give a continuous film, and therefore stiffness
EM 50% ethyl acrylate, 50% methyl methacrylate t o fabric, is by plasticizing it with a softer polymer. I n Table IV
M 100% methyl methacrylate
is shown the effect on fabric stiffness of a physical mixture of poly-
Each was polymerized in a similar system, using an anionic mer dispersions E and M, dried on a t 15OoC.,as compared with
dispersing agent, and to an average chain length in a range where each polymer separately. As the two polymers are compatible,
variations would not be critical; therefore, any marked differences they fuse together to form a single-phase mixture having consider-
between the materials may be attributed to their monomer able hardness and capable of stiffening the fabric appreciably.
composition. By contrast, a mixture of polymer E and an infusible pigment
Cotton sheeting was dipped into the polymer dispersions, (titanium dioxide) forms a two-phase system having the proper-
squeezed, and dried either a t room temperature (ea. 25' C.) or at ties of the soft, continuous phase, and therefore does not stiffen
150' C. Gurley stiffness values were obtained, and the hand the fabric.
was also evaluated subjectively. In addition, portions of each
polymer were dried down in the absence of fabric to determine the
film properties, The data, presented in Table 11, indicate the TABLEIV. EFFECTOF MIXTURESOF EMULSIONPOLYMERS
direct relation between the physical properties of the dried-down Applied Solids Gurley
polymer and the effect on fabric. The soft, rubbery polymer (E) % E % M % Ti02 Stiffness
gives a full, heavy hand with little added stiffness; the stiff, 8 .4. 11
brittle copolymer (EM) produces a stiff, rather crisp finish; 4 .. 28
.. .. 12
but the even stiffer polymer (M), which has such a high fusing 4 .8. 4 11
point that the tiny dispersed particles will not coalesce into a
continuous film, has very little effect on the hand. A polymer
of the latter type, lacking cohesion, may nevertheless have satis- This is an extreme case; most aqueous dispersions for textile
factory adhesion to certain fibers, and in such a case may be used use are of the %ontinuous film" type, and mixtures of these will
to deluster a very shiny fabric. give effects intermediate between those of the components.
Where a polymer such as M is to be used
for delustering, however, it is important
TABLE
11. EFFECTOF CHEMICALCOMPOSITION OF EMULSION POLYMERS not to use it in conjunction with a softer
Drying Gurley polymer which will plasticize it; other-
,Compo- Solids on TErnZ., Stiffness wise stiffness will result, instead of the
Polymer sition Film Form Fabric, % Mg./Inoh Hand of Fabria desired dulling effect. However, the
Water only . . .
. ... .... 25
150
6.1
6.7
Soft
stiffness produced by the mixture of poly-
E 100 E A a Soft, rubbery 4 25 7.5 Full, heavy mers E and M (28 mg. per inch) is not
4 8.9
8 I5O
150 11 HO great as was obtained from copolymer
ERI 50 EA Stiff, brittle 4 25 16 Stiff E M (56 mg. per inch) (cf. Table 11).
50 M M A 4 31
8 150
150 56 CHEMICALPROP~RTIES AND END USE.
M 100 MMA Discontinuous, 4 25 7 5 v: slightly stiff It should be evident that, in so far as
powdery 4 150 8.9 dielustered" the type of finish obtained on fabric is
8 150 12
a EA, ethyl acrylate. MMA, methyl methacrylate. due to the physical properties of the
polymer, any other polymer type hav-
1290 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Vol. 45, No. 6

V. AGINGCHARACTERISTICSO F VARIOUS COPOLYMERS ON COTTON F.4BRICR

TABLE
Effect on Stiffness" Effect on Colora
Oven, 12 Hours a t Fade-Ometer Oven, 12 Hours Fade-Ometer
Fabric
NO.
Polymer Composition Or&
units
-
1200 c.
Units
50 Hours 100 Hours,
% L C Units % i.c Units % i C
orig,, a t 120' C. 50 Hours 100 Hours
units Refl. % d.d Refl. % d.d Refi. % d.d
0 Water 7 6 .. 7 0 7 0 99.2 96.1 3.1 98.2 1.0 96.5 2.7
1
2
Ethyl acrylate
Ethyl acrylate, methyl meth-
11 10 .. 9 I . 11 0 97.2 92.2 5.1 94.9 2.4 94.5 2.8

3
acrylate
Vinyl chloride, 2-ethyl hexyl-
56 61 9 54 .. 69 23 98.5 94.2 4.4 95.1 3.5 94.3 4.3
acrylate 14 29 107 57 307 64 357 96.0 83.5 13.0 80.1 16.6 78.9 17.8
4 Butadiene, acrylonitrile 10 12 20 111 1010 111 1010 88.7 77.6 12.5 64.2 27.7 80.7 31.6
5 Vinylidene chloride, vinyl ace-
tate 46 50 9 58 26 61 33 92.0 77.8 15.4 45.2 50 9 39.8 56.7
6 S7inyl acetate 78 86 10 89 14 89 14 98.3 93.1 5.3 97.0 1.3 96.3 2.0
a Gurley stiffness, mg./inch.
b Reflectance as % of ceramic plate, using blue filter.
Increase in stiffness, as 70of original.
d Decrease in whiteness, as % of original.

ing the same physical properties will tend to produce a simi- Here is shown the effect of eight commercially available aqueous
lar result. Thus, the finishes achieved with ethyl acrylate and dispereions, applied at equal solids (about 6%) to a rayon challis,
methyl methacrylate, in the above examples, may be closely an acetate satin, and a nylon taffeta. The fabrics vere dipped,
duplicated by appropriate combinations of, say, hexyl methacry- squeezed, and dried a t 150°C. The polymers are listed in order
late and acrylonitrile. Moreover, the choice is by no means of relative stiffness on rayon, as ranked subjectively by several
limited t o the acrylics. Using nonacrylic monomers, a range of observers. Also listed for acetate and nylon is the degree of
effects may be obtained from butadiene (soft) and styrene, vinyl crazing, or susceptibility to cracking of the finish, which s h o m up
chloride, or vinyl acetate (stiff). As with the acrylics, the range as a white mark when scraped with the fingernail. Conditions
from hard t o soft may be obtained by interpolymerization or necessary for crazing are that the polymer be brittle and the ad-
mixed homopolymerization, or by incorporation of a nonpoly- hesion be insufficient to withstand the abrading force.
merizing plasticizer. Against such competition, the
choice of an acrylic is often based on more suitable
chemical properties. TABLEVI. ADHESIONOF EMULSION POLYMERS TO VARIOGSFIBERS
Among these chemical properties is resistance to Rayon, Acetate Nylon,
aging, specifically to changes resulting from heat Polymera Film Form Rel. Stiff. Rel. stiff. Crazing Rel. stiff Crazing
and light. I n Table V are presented the results of A Rubbery 2 4 Kone 5 None
B Rubbery 2 3 None 3 None
oven test's (12 hours at 120" C.) and Fade-Ometer C Rubbery 3 5 V. slight 5 None
exposure (50 and 100 hours) on cotton fabric treated D Stiff flexible 5 6 V. slight . . .
E Stiff: flexible 5 6 Slight 4 V. siight
with approximately 8% solids of each of several aque- F Stiff, slightly brittle 8 6 Severe 6 Slight
G Stiff, slightly brittle 8 8 Severe 7 Slight
ous dispersions, including acrylics, nonacrylics, and V Stiff, brittle 8 8 Severe 4 Severe
mixed polymers. The fabrics were dipped, squeezed, a Al! acrylics except V (vinyl acetate) and D and E (mixed).
dried at 1500 c,,and subjected to the accelerated * Stiffness. 0 (untreated fabric); 2 full, heavy; 5 leathery; 8 stiff.
- - tests.
aaina
Only the tn-o acrylics (fabrics 1 and 2) and vinyl
acetate (6) were resistant to stiffening and discoloration on expo- On acetate, the relative stiffness generally follows in the same
sure to heat and light. By contrast, one of the nonacrylics (5) order as on rayon; but on nylon the order is somewhat irregular.
and two mixed polymers (3 and 4) showed marked adverse Attempts to relate the adhesion to the monomer composition
changes as a result of thc accelerated aging tests-in one case within the series illustrated have not been very successful, al-
the fabric stiffness showed more than a tenfold increase, and in though it would appear that the vinyl acetate dispersion, which
another the whiteness (as measured in blue light) showed a drop is so effective on the acetate and rayon, is inferior to the stiffer
to less than half its original value. While no far-reaching con- acrylic on the nylon. The vinyl acetate also shows more crazing
clusions may be drawn from so brief an experiment, neverthe- on nylon than do the acrylics.
less, the data illustrate what has been found to be true in many One factor which complicates the situation is the presence of
other studies: The acrylics invariably have good aging properties, dispersing agent, a component of practically all emulsion poly-
but in mixed polymers they cannot overcome inferior properties mers; because of this, the effects of chemical composition on ad-
imparted by other monomers. The addition of ultraviolet ab- hesion are more easily studied by application from true solution.
sorbing agents and other adjuncts would improve the aging The dispersing agent is also primarily responsible for the ionic
properties of the more unstable materials, but the acrylics are nature of most dispersions, and with the acrylic emulsion poly-
satisfactory without such agents. mers, as with all dispersions, the ionic nature is of considerable
Not shown in Table V are the excellent aging properties of vinyl importance in determining handling properties. The usual an-
acetate-acrylic mixed polymers. Vinyl acetate alone will always ionic form is incompatible with most cationic materials, including
give a stiff fabric; softer finishes based on plasticized or copoly- certain thermosetting resins; the cationic form, ip addition t o
merized vinyl acetate will have aging properties dependent on
being incompatible with anionics, tends to exhaust onto textile
the properties of the plasticizer or other monomer. Some of the
fibers, x-hich may be either desirable or undesirable. The non-
softeracrylics, asmight be expected, are ideal for this purpose, even
though the extent of interpolymerization is believed to be small. ionic dispersions are the most versatile because not only are they
A second property which may be regarded as primarily chemical generally compatible with other finishing agents, but, by addition
in nature is the adhesion of the polymer to the textile fiber. of a suitable cationic surface active agent, they can be made to
It was stated earlier that the type of bodying or stiffening effect exhaust. It is thus not necessary that the polymer itself be
imparted by a polymer depends on its physical form, provided it cationic, in order for exhaustion to take place. The ionic nature
has good adhesion to the fibers, and that in the case of cellulosic must be considered as contributing to the properties of the poly-
textiles the adhesion is usually satisfactory. This is not always meric dispersions, quite apart from the physical or chemical prop-
so with the hydrophobic fibers, as is illustrated in Table VI. erties of the polymer itself.
 June 1953 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY 1291

I n considering the degree of wash-fastness of a thermoplastic degree of nonskid; satisfactory adhesion to the fibers; and no
finish, a distinction, albeit an academic one, must be made between stiffening on storage. I n this application, resistance t o ultraviolet
two factors: the weight retention, which is almost always high, light is not a factor, nor is discoloration on storage.
and the retention of the finish, which in certain instances-e.@;., Similarly, certain of the acrylic emulsion polymers have shown
those depending on adhesion of polymer to fiber-may be ap- considerable merit as binders for nonwoven fabrics. In such an
preciably reduced. For example, washing a fabric which has application the web of textile fibers is held together by the resin
been treated with a moderately hard acrylic emulsion generally binder, which may either be printed on in the form of stripes or
lowers the resin content by less than 10%; but because the ad- other pattern or applied uniformly throughout the fabric. As
hesion between the polymer and the fibers has been partially in the case of rug backing, only the higher cost of the acrylics has
destroyed, the fibers are no longer as completely cemented to- prevented their greater utilization in this use.
gether, and the stiffness may be reduced to a considerable degree. Pigment binding is another field in which the acrylics have
Hot pressing, particularly in the presence of moisture, is helpful shown promise, Any of the acrylics, soft or stiff, may be em-
in re-establishing the adhesion and, therefore, in restoring much ployed to bind dulling agents to obtain combination bodying-
a of the original stiffness. delustering effects. As a component of backfilling mixtures,
This phenomenon is illustrated by the data in Table VII, which ordinarily contain clay plus starch or flour and are used
which show the effects of washing and various aftertreatments to add body, weight, and a closed-up appearance to lowgrade
on the stiffness of an acrylic-treated cotton fabric. fabrics, the acrylics impart a degree of water resistance and free-
dom from dusting. Certain of the acrylics have also shown merit
in reducing crocking when added to pigment dyeing systems con-
TABLEVII. EFFECTO F WASHING AND PRESSING ON FABRIC taining other types of resin binders. I n each of these applications
STIFFNESS the acrylics are especially valuable because of their freedom from
Gurley Stiffness, Mg./Ineh discoloration and from change in stiffness on aging, in addition to
Untreated Acrylic
their adequate binding properties.
Original 6 67 Acrylic polymers have been used to prepare coated fabrics
Washed, air-dried (25' C.) 7 23
Dry-pressed (150' C . ) 7 31 having excellent resistance to weathering, Coatings may be ap-
Sprayed, pressed (150' C.) 6 45
plied from solvent or from thickened water emulsion, and may be
clear or pigmented. By proper selection of monomers, any de-
gree of flexibility may be obtained without need of plasticizers;
The fabric, along with an untreated control, was tumbled in in the same manner the temperature range (between brittle and
a wash wheel for 15 minutes at 60" C. in 0.1% soap and 0.1% tacky) may be modified to suit the specific end use. Adhe-
sodium tetraphosphate, followed by rinsing, centrifuging, air sion to various textile fibers ranges from good to excellent.
drying, spraying with water (where indicated), and pressing The acrylic emulsion polymers, in common with most other
at 150' C. Despite the changes in stiffness, the resin content (by thermoplastics, are ineffective in imparting shrinkage control or
acetone extraction) remained constant a t 7.5% throughout the crease resistance, generally cause a slight increase in tensile and a
series. slight decrease in tear strength, but usually improve the resist-
The possibility of soap pickup on the fabric cannot be com- ance to abrasion. The resistance to flat abrasion, in particular,
pletely ruled out as a contributing factor t o both weight retention is often markedly improved. Table VI11 gives typical data on the
and softening of the finish. Nevertheless, in other instances effect of several acrylic polymers on the properties of a cotton
where nonionic detergents have been used in washing, the resin sheeting; an 8% solids application was employed to emphasize the
content has rarely dropped more than 10% in a single wash; results.
yet there is always some loss of stiffness on tumble washing,
and partial regain on damp pressing, even when water alone is WATER-SOLUBLE ACRYLICS
used as the washing solution. Thus, the variation in stiffness is Thus far, only the water-insoluble acrylics, which are avail-
due to changes in adhesion (and possibly cohesion) rather than able in a wide range of physical forms, have been considered.
t o loss of polymer. By contrast, the soluble acrylics-the acids, salts, and amides-
The full hand imparted by the softer acrylics undergoes a simi- with few exceptions dry down to hard, stiff films, by virtue of the
lar, though less noticeable, change on washing and pressing. fact that the same strongly polar forces that draw the molecules
into solution will, in the absence of water, bind the molecules
OTHER USES OF WATER-INSOLUBLE ACRYLICS
together to form glassy solids having little thermoplasticity.
During World War I1 the problem of keeping drinking water Applied to cellulosic fabrics, each imparts a crisp, starchlike
cool in the field was solved by the use of a heavy canvas water finish. Because they remain water-soluble (except in certain
bag, so impregnated as to prevent leakage but to permit a cases), they are not widely used as finishing agents, although
slow diffusion of water to the surface, where evaporation exerted sodium polyacrylate is frequently used as an additive to starch
a cooling effect on the contents of the bag. This controlled formulations to impart greater toughness and flexibility.
seepage was attained by use of an acrylic polymer in com- Of greater importance is their use in sizing warp yarns to pro-
bination with a hydrophilic colloid. The proper diffusion rate tect them during weaving; in this application ready removability
and flexible &ish could no doubt have been obtained with other is an asset. The function of a warp size is to hold down the loose
polymers; the choice of the particular acrylic was based on fibers and protect the yarn from chafing during weaving. The
chemical inertness, freedom from toxicity. - , and re-

sistance to change' on storage or exposure to light.

A potentially important use for the acrylics is that TABLE VIII. EFFECTOF ACRYLICS ON FABRIC PROPERTIES
of rug backing. The function of such material is to Grease
bind the pile fibers and/or to prevent the rug from
ShrinkageQ, RgZo&;b, Elmendorf Tensilec, Abrasio n
Polymer % Tear, Warp, TBL
skidding on a polished floor. Although as yet not 8% Asslied dolids Waru Fill Waro Fill Wars. Lb. Lb. CYOl&
widely utilized in this application because of their Untreated 8 . 8 6 . 1 65 61 3.8 45 7 700
relatively high price, the softer acrylics have all the
E EA)
Eih (EA/MMA)
M (MMA)
6.0
6.0
6.7
5.7
5.3
5.8
i: 54
66
48
58
3.2
2.7
2.8
47
53
44
29 '800
20 500
16,900
:
necessary attributes: flexibility without need of a Full Sanforize wash, 40 minutes at 80° C.in 0.1% soap.
@

plasticizer, thus eliminating the possibility of stained 6 Monmnto test.

C 1 inch raveled strip.
floors through plasticizer migration; any desired
1292 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 45, No. 6

sizing agent must, of course, form a tough film, neither too brittle
nor too soft; but not all polymers having satisfactory physical T.4BLE Ix. REACTIOM
O F POLYlCRYLIC ACID WITH N Y L O N
properties will make good sizes. Unless the polymer has suffi- Baked 10 Amount Applieda, Retained after Retained,
Polymer Min. a t C. G. Washingb, G. %
cient adhesion to the fiber, it will flake off when subjected to the PAA 115
flexing and abrading forces incurred during weaving. 175
PLIA 115
There are many materials which could be used in the warp
sizing of cotton; various starches, sodium carboxymethylcellu-
lose, polyvinyl alcohol, and sodium polyacrylate are a few of the
many which have sufficient adhesion, in addition to the necessary
film properties. Polyacrylic and polymethacrylic acids would
also be satisfactory, except that they are too acidic and would out by extracting the treated fabric with boiling benzyl alcohol,
tend to degrade the cellulose. Because cornstarch, plasticized a nylon solvent. This will dissolve away the unreacted nylon,
with tallow or other softener, is both efficient and economical, leaving a gossamerlike residue of the polyacrylic acid-nylon
it is the most widely used material for sizing cotton warps. The reaction product. In a typical instance, There the amount of
only acrylic having any appreciable commercial utility in this polyacrylic acid applied was 5% (on the weight of the nylon),
application is sodium polyacrylate, which to date has been em- the residue amounted to 9.8%. It contained both nitrogen and
ployed only as an additive to starch mixes. unreacted carboxyls.
In the sizing of nylon, however, the situation is different. The The mechanism of the reaction has not been determined: two
various starches, sodium carboxymethylcellulose, and sodium possibilities are (1) imide formation and (2) trans-amidixation.
polyacrylate do not have sufficient adhesion to nylon, and tend to
flake off. Polyvinyl alcohol, generally employed with boric acid HOC=O
or borax, has slightly better adhesion, and has enjoyed consider-
able use in this application. More recently it has been found
K R'-(nylon)
I
+ (PAAjL(PA 41
that polymethacrylic and polyacrylic acids have excellent adhe- H
sion, Both show up well in laboratory tests, but on a plant
scale the polyacrylic has demonstrated a definite superiority and
is probably the most effective of the currently available nylon
sizes.
The reasons for the superiority of polyacrylic acid over poly-
methacrylic and the other materials have not been clearly eluci-
dated, but the following factor8 are suggested:
Both of the acrylics are rather strong acids, which could ac-
count for their great specific adhesion to nylon. Polyacrylic
acid is somewhat stronger than polymethacrylic acid.
The polyacrylic acid molecule is contracted into a coiled
configuration, so that solutions of polyacrylic acid have a lower
viscosity than would be expected from the degree of polymeriza-
tion. Polymethacrylic acid exhibits this property to a lesser
degree. The lower viscosity a t a given concentration facilitates The latter seems much more plausible. There is a third pos-
penetration into the yarn, resulting in more complete bonding sibility-that the combination takes place on end groups; the
o! the individual fibers by mechanical as well a9 specific adhe- final result would be similar to Reaction 2 .
sion. Aside from the theoretical aspects, tLyo practical considera-
The coiled chain should also confer greater flexibility to the
polymer and lessen its tendency to flake off. From steric con- tions are worth mentioning. First, when polyacrylic acid is used
siderations, a polyacrylic chain should be more flexible than a as a warp size, it should not be subjected to severe drying condi-
methacrylic of equal length. tions; otherffise it will not be completely removed in mashing.
On the basis of present information, it is difficult to determine Second, if sufficient heat is applied, it should be possible to
the exact significance of each of these factors. For example, utilize polyacrylic acid as a durable finishing agent. Data pre-
partial neutralization of polyacrylic acid with sodium hydroxide sented in Table X show that this is so. The polyacrylic acid was
to the extent of 20 to 25% is known to interfere with its efficiency applied to nylon taffeta by dipping and squeezing to obtain 5 %
as a nylon size. It cannot be stated, however, that this is due solids on fabric. Baking a t temperatures up to 176' C. was con-
entirely to the decrease in acidity, for neutralization is accom- ducted in an oven; for the 200" treatment a thermostatically
panied by a straightening of the polymer chain, with resulting controlled hot iron Tas used. Washing was conducted a t 80' for
increase in viscosity and decreased flexibility. On the other hand, 40 minutes.
the flexibility of the polymer is probably not as important as the Because nylon is heat-set a t temperatures around 200" C.,
other two factors, as it is possible to neutralize the acid with a it is possible to utilize polyacrylic acid as a warp size, then fix it in
material-e.g., triethanolamine-which, by acting as a plasti- the fabric as a durable finish. For a crisp organdy finish,
cizer, will increase the flexibility of the film, yet still interfere with hon-ever, the polyacrylic acid is best applied to the woven fabric,
sizing efficiency because of adverse changes in the other factors.
The probability that the efficiency of polyacrylic acid as a size
for nylon is due primarily to greater specific adhesion, rather than x. EFFECTO F HEATO N DURllBILITY
TABLE O F POLYACRYLIC
to physical properties of the polymer, is etrengthened by the ACID ON KYLON
finding that polyacrylic acid may be made to combine chemically Heat Treatment Girley Stiffness, JIg./Inch
xvith nylon. Polymethacrylic acid has a much lover degree of Min. Temp., O C. Unwashed Washed % Retained"
reactivity. I n Table IX are shown data obtained on drying 10 120 16 1 fi
5 150 19 3 16
measured amounts of polyacrylic acid or polymethacrylic acid 30 150 17 12 71
onto nylon fabric a t elevated temperatures and determining the 1 173 17 3 18
10 173 19 16 84
quantity retained after a scour in 0.1% soap and 0.1% soda ash 0.08 200 18 11 61
0.5 PO0 17 17 100
for 40 minutes a t 80" C.
a untreated fabric (about 1 t o 2 mg./inoh) ,
Not corrected for rtiffness of
The possibility that the 175" baking is merely insolubilizing which was not altered by heat treatment or washing.
the polyacrylic acid through anhydride formation can be ruled
 June 1953 INDUSTRIAL AND ENGINEERING CHEMISTRY 1293

so that all the yarns, both warp and filling, are sized. The treat- ferrous sulfate was dried into wool, and the wool worked for
ment is particularly effective for stiffening nylon lace. several hours a t 95” C. in a dispersion of methyl methacrylate,
Further data, outside the scope of the present paper, indicate which in some instances contained 0.03% hydrogen peroxide.
that polyacrylic acid/glycerol (10 to 3) will give a finish of even At 45% add-on the area shrinkage was reduced from 50% (for
greater crispness and durability than polyacrylic acid along, the the untreated) to 0.5% for the treated. The investigators be-
glycerol apparently not only acting to cross-link the polyacrylic lieved the shrink resistance to be due to internally formed poly-
acid molecules, but serving as a flux or solvent medium for mers. Weight gains up to 240% were reported, but no doubt
the reaction with nylon. The finish is exceedingly resistant much of this was due to surface resin.
to removal by 1 % hydrochloric acid or 1% sodium hydroxide a t I n another case (II), wool fabric, saturated with dilute persul-
the boil. Unfortunately, polyacrylic acid does not have durable fate solution, was exposed to the vapors of various monomers a t
adhesion to Orlon or Dacron. 90” to 95” C. Effects noted were shrink resistance, decreased
affinity for water vapor (possibly because available sites were
OTHER USES OF WATER-SOLUBLE ACRYLICS
blocked by the polymer), and a fuller hand (perhaps due in part
to surface resin). I n other studies (5),wool fibers containing poly-
The alkali salts of polyacrylic and the polymethaorylic acids methacrylamide were aftertreated with formaldehyde to obtain
exhibit in water solution the high viscosity expected of a poly- a cross-linked polymer, a t least partially within the fibers. Re-
meric material. Sodium polyacrylate, at present the most duced extensibility resulted.
readily available salt, finds considerable use as a thickener for More recently, a study of polymerization of vinyl monomers
natural and synthetic latices, as an ingredient in printing pastes, within viscose rayon fibers has been reported by Landells and
and 8s a dispersing agent and protective colloid. It is compatible Whewell (4). Weight gains up to 78% are claimed; the proper-
with most anionic and nonionic dispersions and, unlike many ties of the cellulose are said to have been considerably altered,
natural gums, is unaffected by bacterial or hydrolytic decom- but no details are given.
position. The above possibilities are of course not limited to acrylics.
Polyacrylamide and polymethacrylamide also tend to be water- Theoretically any vinyl monomer or combination of monomers
soluble. Viscous solutions of the latter may be made by poly- may be utilized in this way, although from a practical standpoint
merization of the commercially available monomer in aqueous each will probably require its own special conditions for greatest
medium a t temperatures below 80” C. Polymethacrylamide pre- yield.
pared under other conditions may be incompletely soluble I n addition to polymer formation, it is also possible to obtain
(10). reaction of the monomer with the fiber. Thus, Stallings (IS)
Films of the polyamides, unlike those of sodium acrylate or treated cotton fabric with acrylonitrile in the presence of sodium
methacrylate, may be insolubilized by heat, which causes cross- hydroxide to obtain cyanoethylcellulose. The fabric was said
linking of the polymer chains through imide formation. Of to be stronger, stiffer, less water-absorbent, and more resistant
greater technological importance is the very complete insolubili- to abrasion. Under other reaction conditions, sodium carboxy-
zation which may be obtained by reaction with formaldehyde, ethylcellulose was obtained ( l a ) ,and the fabric was stronger and
glyoxal, or various amino- or phenol-formaldehyde condensates. more water-absorbent, and had a linen-like luster. The variation
Such combinations have the properties usually associated with in water absorption reflects the increased hydrophilic tendency of
polymeric thermosetting materials, and may be used to obtain the functional group, going from cyanoethyl to hydroxyl (in the
such typical effects as durable crispness, stabilization of cellu- original cellulose) to sodium carboxyethyl.
losic fabrics against shrinkage, durable glazing, and embossing. None of the above processes involving monomer applications
Ammonium polyacrylate has similar thermosetting properties, has as yet attained commercial importance.
but to a much lesser extent. Sodium polyacrylate, when made by
hydrolysis of acrylonitrile, may contain a small proportion of ACKNOWLEDGMENT
amide or ammonium groups, but not to the extent that it is easily
insolubilized by formaldehyde or heat. Credit is extended to R. F. Crawford and to Betty Haffner
It is possible to prepare copolymers of methacrylamide with for their valuable contributions to the experimental sections of
acrylic and methacrylic acids and esters, as well as with a variety the paper.
of nonacrylic monomers, The water solubility of such products
varies with the proportion of hydrophilic groups and the degree LITERATURE CITED
of polymerization, and no general rule can be given (IO).
I
(1) Am. SOC.Testing Materials, “ASTM Standards,” Part 5, p.
1580, 1949.
MONOMER APPLICATIONS (2) Conant and Liska, J . Appl. Phys., 15, 767 (1944).
(3) Institute Paper Chemistry, P a p e r Trade J., 104, No. 21, 4 3 ;
I n the applications thus far discussed, the acrylics have been No. 22, 4 3 (1937).
prepolymerized and have therefore been unable to penetrate the (4) Landells and Whewell, J . Soc. D y e r s Colourists, 6 7 , 338 (1952).
fibers. In many instances, however, it is possible to apply an (5) Lipson and Speakman, Ihid., 6 5 , 3 9 0 (1949).
acrylic in the form of the monomer and polymerize it, at least in (6) Lipson and Speakman, N a t u r e , 157, 590 (1946).
part, within the fibers. A number of researches along this (7) Neher, IND.ENG.CHEM.,28, 267 (1936).
line have been reported, and several of these are briefly outlined (8) Rehberg and Fisher, Ibid., 40,1429 (1948).
below. (9) Rehberg and Fisher, J . Am. Chem. SOC.,66, 1203 (1944).
The methods of application are varied. Depending on the (IO) Rohm and Haas Co., Technical Bulletin “Methacrylamide,”
1950.
physical form, solubility, and vapor pressure of the monomer, (I 1) Speakman and Barr (to Imperial Chemical Industries), Brit.
each of the acrylics may be applied in several of the following Patent 559,787 (1944).
ways: from water or solvent solution, from emulsion, as the pure (12) Stallings (to Rohm & Haas Co.), U. S. Patent 2,390,032
liquid, or in the vapor phase. The catalyst, which is generally (1945).
applied to the fiber in a separate operation, is usually a persulfate (13) Ihid., 2,473,308 (1949).
or peroxide type, sometimes in combination with a ferrous salt or
RECEIVED for review August 6, 1952. ACCEPTEDOctober 23, 1952.
other activator. Presented before the Division of Paint, Varnish, and Plastics Chemistry,
Speakman and coworkers have made numerous investigations Symposium on Resins in Textile Finishes, a t the 122nd Meeting of the
of monomer applications to wool. I n one instance (6), 0.2% AMERICAN CHEMICAL SOCIETY,Atlantic City, N J.