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Патент USA US3067152

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' United 5tates Patent .0 "me
2 .
laundering purposes with an N-vinyl-Z-oxazolidinone
polymer of the general structure:
Wilhelm E. Walles, William F. Tousignant, and Lamar C.
Cloninger, Midland, Mich., assignors to The Dow
Chemical Company, Midland, Mich” a corporation of
o Dra
. Fil
' e dF eh . 24 1958 Ser. No. 716 868
9 Claims. (03252-1111)
Patented Dec.
ma )5...
\ .
wherein Q and Z independently are hydrogen or methyl,
10 with the limitation that at least one of said substituents
The present invention contributes to the art of launder
is methyl, and‘ y is a plural integer of considerable mag
ing and cleansing textile goods. It‘relates to a com
position and method for washing and laundering textile
materials, particularly mixtures of fabrics and the like
textile goods that have been dyed di?erent colors and
particularly in the washing together of colored and white
nitude, such as one that is in excess of 10 and usually
in excess of 100 or so to as high as 1,000—2,000 and
" laundering.
contain in the admixture only a minor proportion of the
N-vinyl-Z-oxazolidi'none polymer with the synthetic de
fabrics so as to avoid the undesirable e?ects of “dye m1
gration" from one fabric to another, especialfy from
colored fabrics to white ones during their simultaneous
Advantageously, the composition is prepared so as to
tergent or soap constituent. More advantageously, the
composition is comprised of between about 0.1 and 15
When textile fabrics and the like (including cloth and
other textile manufactures) are being washed or laun
dered in domestic or commercial installations, it is ordi
narily considered prudent to separate the white and
colored goods and to wash them in individual batches.
The reason for this, as is well known, is that many
colored or dyed textile fabrics tend to release small quan
weight percent, preferably from about 2 to 6 percent,
based on the weight of the soap or detergent in the com
position, of the incorporated N-vinyl-Z-oxazolidinone
polymer. The quantity of the polymer of Formula I
incorporated in the laundry composition is relatively im
material, as a general rule, so long as an amount is pro
vided therein which is adequate to materially prevent dye
migration during the laundering operations in which it
is employed and the composition contains an adequate
quantity of the soap or detergent to accomplish the in
they are cleansed. Such released dyestuff is likely to be
absorbed'by other fabrics or textile goods that are present 30 tended laundering purpose. V _ _
While it is generallyv bene?cial tdiihesasis ordeterl'
in the same wash liquid. As a result of this dye migra
gent to be utilized in powder, ?ake or liquid form, such
tion or dye bleeding, white and light colored fabrics/and
materials in solid form (that is to say in other than
other goods are likely to be stained to such a degree that
powders or the like ?nely divided bulks and ?akes) may
they are spoiled and may have to be discarded
also be prepared in accordance with the present inven
The overcoming of such a situation in laundering oper
tion. Thus, bar soaps and detergents may be so con
ations would be of important practical signi?capce. It
stituted with marked advantage. As is indicated in the
would be a boon not only to housewives, but to com
foregoing, the N-vinyl-Z-oxazolidinone polymer may be
’ mercial laundries as well. Tremendous amounts of tex
tile materials, including fabric, clothing, bedding, table 40 incorporated in and mixed with any desired soap or de
tergent material conventionally employed for domestic
coverings, towels and other goods are washed daily.
and commercial laundry purposes. As an illustration.
Considerable quantities of soap and synthetic detergents
any of the detergents suitable for such purpose that are
are required and employed for such purposes. Many
mentioned in “Synthetic Detergents and Emulsi?ers-Up
remedies for dye-bleeding have been suggested. For ex
Date 111" by John W. McCutcheon, printed in 1955,
ample, acetic acid is frequently used to prevent bleeding
of dye from colored woolen fabrics. Furthermore,dye 45 by McNair-Dorland Co., Inc., of New York and re
printed from “Soap and Chemical Specialties” for July,
stuff manufacturers have been diligent in their e?'orts to
August, September and October 1955, may be utilized.
produce washfast dyes capable of being more strongly
These include those under the trademarks “Dreft” (made
bonded or attached to the ?bers colored therewith. De~
from a base of the sodium salt of lauryl alcohol sul
spite this, however, a completely e?’ective solution to the 50 fonate), “Fab” (an alkyl aryl sulfonate plus binders),
tities of the dyestu? during a washing process wherein
problem involved has not heretofore been proposed or
made available.
It would be advantageous, and it is the chief aim and
concern of the present invention, to provide a new and
“Glim,” “Joy,” _“Oxydol," “Tide,” “Trend” (an alkyl
aryl sulfonate plus binders), “Vel", (the ammonium salt
of a sulfated monoglyceride). and the like. Likewise,
handled basis.
In accordance with the practice of the present inven
titles and concentrations of the soap or detergent that
tion, an improved composition for the washing of mixed
achieve the desired washing and laundering action.
The method of the present invention comprises adding
to an aqueous washing or laundering bath for textile
conventional laundry soaps which, chemically, are ‘com
highly e?icacious composition and method for the wash 55 binations of fats (such as palrnitin, stearin, olein, etc.)
with alkalis (i.e., sodium for solid soaps and potassium
ing and laundering of textile fabrics that would permit
for liquid soaps), including "Ivory" (neutral soap of
mixed handling of various colored fabrics and other dyed
high purity made from specially selected oils and fats),
textile goods in the same washing bath as well as the
“Lux," “Fels-Naphtha,” and the like or equivalent soaps
simultaneous washing as a single batch in the same bath
of white and colored textile materials without di?iculties 60 may also be utilized in the practice of the present inven
tion. As indicated in the foregoing, ‘the compositions
of the indicated and well known variety due to dye mi‘
should contain an adequate quantity of the soap or de
gration or bleeding. It would be a corollary advantage
tergent to permit their use in the'conventional manner
of commensurate magnitude and it is also an object of
Those who are skilled in the art will have little
the invention, to provide such a composition and method 85 thereof.
di?iculty in determining suitable proportions for meeting
capable of being utilized on an economical and easily
such end, taking into account the normal desired quan
batches of colored or colored and white textile fabrics 70
and_other textile goods comprises a mixture of a syn
thetrc detergent or soap material suitable for conventional
are_required in the wash liquid in order to effectively
fabrics a quantity of an N-vinyl-2-oxazolidinone polymer
of the above described type 3
in proportions consistent with
those indicated in the foregoing and performing the wash
ing operation with the bene?t of such composition.
Practice of the present invention permits colored fab
indicated bene?ts and realize the desired ends. Advan
tageously, the normally solid polymer that is utilized as
a dye absorbing agent for the present purposes is a high
polymer having a Fikentscher K-yalue of at least about
rics or colored and white fabrics to be washed together
in the same laundry treatment with substantially if not
completely minimized dye bleeding or dye migration and
practically complete, if not entire, avoidance of fabric
staining due to such causes. This simpli?es the washing
operation considerably and saves time, e?ort, water and
detergent or soap for the purpose. The invention is
adapted to be practiced on either the domestic or com
mercial level with equal-,e?ectiveness and bene?t. The
washing may be accomp ished with bene?t of practice of
More advantageously, the ‘-N-vinyl-2-oxazolidinone
polymer employed has a Fiken cher K-value between
about 10 and 100.. Most advantageously, its K-value is
from about 10 or 15 to 75. 'IhdFikentscher K-va-lue of
a polymeric substance is a quantity, as has been de?ned
by Fikentscher in “Cellulosechemie" 13, 60 (1932), that
represents an approximate measure of the weight frac
tion of a given sample of polymer in an in?nitesimal
molecular weight range. According to a concept that is
widely acceptable to those skilled in the art, it may be
the present invention ev u when oxygen, chlorine or other 15 said in corollation in an exponential manner, to the mean
bleaches are employed in the soap or detergent-contain
average molecular weight that obtains in a given sample
ing wash liquid or when water softeners, including poly
phosphates etc., are incorporated in the wash water to
facilitate its cleansing action.
of a polymer susbtance.
The N-vinyl-Z-oxazolidinone polymers that are utilized
in the practice of the present invention are moderately
The N-vinyl-2-oxazolidinone polymers are adapted to 20 hygroscopic polymeric materials. PVO-M is readily
accomplish the indicated advantages by reason of their
soluble in water, in any concentration, excepting that it
exceptional’af?nity for and preferential absorbing ability
exhibits an inverse solubility phenomenon in plain water
of dye-stuffs of practically all classes, including vat, soluble
at temperatures commencing at about 40° C. However
vat, sulfur, acid, basic, direct, the various metallized dye
the presence of soaps or synthetic detergents in the water
stuffs, etc. Such dyestuffs, by way of didactic illustra 25 ordinarily‘ tends to raise the cloud point of PVC-M to a
tion, as Brilliant Green Crystals, Sulfanthrene Redv 3B,
substantial degree and frequently result in the complete
. Amacel Scarlet BS, Naphthol ASMX, Fast Red TRN
Salt and lmmcdial Bordeaux G are readily absorbed by
the N-vinyl-Z-oxazolidinone polymers. Other dyestuffs,
avoidance of such phenomenon. Despite the solubility
or insolubility of the anti-dye bleeding polymeric agents
used in the practice of the present invention, satisfactory
by way of further illustration, that are readily assimilated 30 results are obtained at any temperatureof operation. It
by the polymers include such mordant-acid dyes as Ali
is relatively immaterial whether the -N-vinyl-2-oxazoli
zarine Light Green GS and Brilliant Alizarine Sky Blue ~dinone polymer is in solution or not, since the dye at
BS PAT; such basic dyes as Brilliant-*i‘Green Crystals,
tracting polymers are satisfactorily operative and effective
Du Pont Methylene Blue ZK, and Rhodamine B Extra
eitherfgsituation. Furthermore, especially under laun
S; such vat dyestuffs as Midland Vat Blue R Powder, 35 dering conditions, the usual agitation of the wash baths
Sulfanthrcne Brown G Paste, Sulfanthrene Black PG
[tends to maintain the polymer in uniform dispersion there
Dbl., Sulfanthrene Blue 28 Dbl. Paste'and Sulfanthrene
,through even under conditions when it is insoluble there
Red 313 Paste, Indigosol Green IB Powder, a soluble vat
in. The polymeric agents are easily and readily rinsed
dyestuff; such acetate dyes as Celliton Fast Brown 3RA
49. from the washed fabrics in the course of the conventional
Extra CF, Celliton FastRubineBACF, ArtisilDirect
Black FKZ, Artisil Direct Navy SR, Artisil'Direct Red
"washing'operation during their laundering; 'No difficulty
3BP, Celanthrene Pure Blue BRS 400 percent, Celanthrene
Red 3RB Conc., Acetamine Orange 3R Conc. and Acet
none polymer on the fabric or other textile goods that
amine Yellow N; B-Naphthol<—24chloro—4-nitroaniline,
an azoic dye; such sulfur dyes as Katigen Brilliant Blue
GGS High Conc. and Indo Carbon CLFS; and premetal
lized dyestu?s including Cibalan Yellow GRL and Supra
lan Blue NB and the like.
In this regard, insofar as the present invention is con
is experienced with residues of the-N-vinyl-Z-oxazolidi
have been treated.
PVC-M is generally obtainable as a white powder
which is free from perceptible odor. PVO-M is dis
closed in the copending application of Wilhelm E. Walles,
William F. Tousignant and Thomas Houtman, Jr., having
Serial No. 696,317 (now US. 2,919,279) which was ?led
on November 14, 1957, for “N-Vinyl-X-Alkyl-Z-Oxazol
cerned, the N-vinyl-Z-oxazolidinone polymers may liter 50 idinone
Compounds.” Besides their excellent capabilities
ally be characterized as functioning in the laundry baths
or minimizing dye bleeding in the practice
as “liquid ?bers" due to the manner in which they act in
of the present invention, the N-vinyl-Z-oxazolidinone
competing with the insoluble ?bers of the textile material
polymers have other bene?cial effects on the soap or
for assimilation of the migrating or bleeding dye colors‘.
detergent wash formulations in which they are incor
In this way, the N-vinyl-Z-oxazolidinone polymer prefer 55 porated.
For example, they exhibit a pronounced tend
cntially absorbs the dyestuffs to prevent them from stain
ency to reduce the irritating and sensitizing propensity
ing other fabrics.
towards human skin of most of the synthetic detergent
Although it has been suggested to utilize other water
laundry compositions. In addition, due to their slight
soluble polymer resins as dyestripping agents, employ
hygroscopicity, their compatibility with washing powders
rnent of these compounds for the purposes of the present 60 of either the soap or synthetic detergent variety is excel
invention has been found to be relatively ineffective and
unsatisfactory. Thus, poly-N-vinyl-2-pyrrolidone (PVP)
the invention, several
is mentioned as being capable of preventing dye bleeding
pieces of cotton fabric having individual dimensions of
in “Melliand’s Textile Berichte” 32, 53-56 (1951). In
2 x 4 inches obtained from a light sheeting grade of
particular, the use of PVP does not provide results at all 65 regular quality stock were dyed in the conventional man
near commensurate with those which may be obtained
ner to a dark blue shade of color with Direct Black AT
through use of the N~vinyl-2-oxazolidinone polymers in
(no Color Index), a direct dye obtained from General
the practice of the present invention.
Dyestuif Company division of General Aniline 8: Film
As indicated, either poly-N-vinyl-S-methyl-Z-oxazolidi
Company. Each of the samples of dyed fabric were then
none (PVO—-M, wherein Q in Formula I is methyl and 70 attached to separate 2 x 4 inch pieces of standard test
Z is hydrogen), or poly-N-vinyl-4~methyl-2-oxazolidi
fabric which were made up of individual ribbons of cloth
none (wherein Z in Formula I is methyl and Q is hydro‘
prepared separately from wool, viscose rayon, silk, cotton,
gen) that are equivalent for the present purpose may be
acetate rayon and nylon. Each of the pieces of dyed
utilized as the dye absorbing agent in the composition
cotton goods and the test fabrics were then given a
and method of the present invention in order to attain the 75 standard washing test in a launderometer according ‘to
of sodium hypochlorite bleach or pyrophosphate water
A.A.T.C.C. Wash Test No. 2. In this test the fabric to
be tested and the washing solution are tumbled together
in a jar containing steel balls for 30 minutes at 120‘ F.
A bath factor (weight ratio of washing solution to fabric)
of about 50:1 was employed. Each of the washing solu
softener ("Calgon"), or both.
of textile fabrics and goods dyed with other varieties of
dyestutfs, including any of those or their equivalents men
tions were prepared with 0.5 percent by weight, based
‘on the weight of the solution, of "Ivory" soap. One of
the test samples designated “A” was subjected to the test
with an unmodi?ed solution of the soap. Another, desig
tioned in the foregoing and conventionally employed for
the coloration of textile materials such as Amacel Scarlet
BS, an acetate dye (American Prototype No. 244) and
Calcodur Pink 2BL, a direct dye-(Color Index 353).
By way of still additional illustration, a separate mix
ture of soap powder (“Ivory Snow”) was mixed in a ratio
of about 10 parts of soap powder to one part of polymer
with PVO—-M. This mixture remained free-?owing and
entirely useable even after having been left in shallow
depths in open beakers for periods of a month under
nated sample “X" was washed with a solution containing
0.05 percent by weight of K-20.2 PVO-M. For pur
poses of comparison, a third sample (sample "2") was
washed in the soap solution containing about 0.05 per
cent by weight of X-30 P . After completion of the
wash tests, each of the samples were carefully examined
for evidence of dye migration or discoloration in the
ribbons of diverse fabric attached to the dyed cotton
conditions of normal humidity (about 50-60 percent
-., cloth. The results are set forth in the following Table I.
. Effect of N-Vinvy-Z-Oxazolidinone Polymers in
Results similar to the foregoing are also obtained when
the present invention is practiced to launder with any
textile cleansing soap or synthetic detergent other varieties
agerage relative humidity at room temperature).
20 'contrast, when the same formulation was made with PVP,
the composition converted to a hard, unuseable block
within about 10 hours as a result of moisture pick-up
Minimizing Dye-Bleeding
from the air by the highly hygroscopic polymer.
Since many changes and alterations in the practice of
26 the present invention can be entered into without depart
ing from its intended spirit and scope, it is to be under
stood that all the foregoing speci?cation and description
be interpreted as being illustrative and demonstrative of
the invention and not limiting thereof.
What is claimed is:
» 1. A detergent composition consisting essentially of
1 0 indicates no color ensign:
(1) a textile cleansing detergent material for laundry use
selected from the group consisting of fatty acid soap and
synthetic organic non-soap detergents that are adapted for
laundry use and (2) between about 15 and about 0.1
weight percent, based on the weight of detergent in the
composition, of a water-soluble N-vinyl-Z-oxazolidinone
polymer of the structure:
As is apparent from the foregoing, the dye in the
, cotton blank bled onto the viscose rayon and cotton but
i did not migrate into the other test fabrics. The use of
PVP did not alter this undesirable dye migration. On the
other hand, PVO-M prevented the bleeding ‘almost
completely. It should be taken into account’ithat the
physical attachment of the test samples introduced a rela
tively rigorous condition of testing.
In order to further illustrate the invention, the fore
going experimentation was duplicated excepting to con
duct the wash tests under more severe conditions at
where Q and Z are independently selected from the group
In addition, according to 45 consisting of hydrogen and methyl with the limitation that
A.A.T.C.C. Wash Test No. 3, about 0.2 percent by weight
at least one of said substituents must be methyl and y is
of sodium carbonate (Na,co,) -was added to each of the
an integer having a positive value of at least about 10.
'wash liquids which contained the same quantities of soap
2. A solid composition according to claim 1.
and polymer additive (excepting for the blank). The
3. A liquid composition according to claim 1.
results are set forth in the following Table II.
4. The detergent composition of claim 1, wherein said
N-vinyl-Z-oxazolidinone polymer is poly-N-vinyl-S-meth
160° F. for 45 minutes.
Effect of N-Vinyl-Z-Oxazolidinone Polymers in Minimiz
ing Dye-Bleeding Under Severe Conditions of Washing
5. A ?ake composition according to claim 2.
6. A powder composition according to claim 2.
1. In the method of laundering colored textile ma
terrals and goods dyed with a dyestu? selected from the
group consisting of vat, soluble vat, sulfur, acid, basic,
direct and metallized dyestuffs in an aqueous wash bath
with a textile cleansing laundering agent in said bath
selected from the group consisting of soap and synthetic
Dark Blue._
Dark Blue.
non-soap detergents that are adapted for laundry
n i
Acetate Rayon
use, the improvement comprising adding to said wash
bath during said laundering between about 0.1 and 15
1 X indicates complete disintegration of test tsbrlc.
65 percent, based on the weight of the laundering agent in
said wash bath, of a water-soluble N-vinyl-Z-oxazolidinone
As is apparent, the PVP was not e?ective for viscose
polymer of the structure:
or cotton even though it was moderately effective for
silk and slightly etfective on the acetate rayon. The
PVO-M was entirely e?ective for silk and acetate rayon
and fairly e?ective for viscose rayon and cotton. It 70
should be borne in mind, incidentally, that the usual
laundering conditions are much milder than those elfected
Viscose Rayon. ........... -
Dark Blue-. Very Light
Dark Blue.
in. the foregoing very severe tests.
Identical results are obtained when the above tests are
wherein Q and Z are independently selected from the
repeated with wash liquids containing normal quantities 75 group consisting of hydrogen and methyl with the limits
?on that at least one of said subst'ituenta must be methyl
218g“: 1i; an integer having a positive value
at 1638i
. 8_ The method “claim 7, wherein said N-viuyl-Zoxazondinom polymer is addcd a: me start of said 5
References Cited in the ?le of this patent
9. The method of claim 7, wherein said N-vinyl-2-
Dicey"! ----------- -- nec' 31' 1957 l
vital“ ---------------- Feb- 17' 1959 ‘
Walles et a1. .......... -- Dec. 29, 1959 ‘
oxazolidinone polymer is poly-N~vinyl-5-methyl-2-oxazolidinone.
Bclgillm, ------------- -- Apr. 14, 1951
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