U.S. patent number 3,816,229 [Application Number 05/218,024] was granted by the patent office on 1974-06-11 for plural coated pile fabric.
This patent grant is currently assigned to Minnesota Mining and Manufacturing Company. Invention is credited to Chester J. Bierbrauber.
United States Patent |
3,816,229 |
Bierbrauber |
June 11, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
PLURAL COATED PILE FABRIC
Abstract
Process for treating pile fabrics with fluoroaliphatic radical
containing compositions in two steps to provide enhanced dry soil
resistance and minimize stain bloom, and the treated pile fabrics
from the process. The first treatment covers the pile substantially
completely, and the second coating, which may comprise organic or
inorganic adjuvants, is applied to the outer 25 percent or less of
the pile.
Inventors: |
Bierbrauber; Chester J. (Saint
Paul, MN) |
Assignee: |
Minnesota Mining and Manufacturing
Company (St. Paul, MN)
|
Family
ID: |
22813448 |
Appl.
No.: |
05/218,024 |
Filed: |
January 14, 1972 |
Current U.S.
Class: |
428/96;
427/412 |
Current CPC
Class: |
D06M
15/277 (20130101); Y10T 428/23986 (20150401) |
Current International
Class: |
D06M
15/277 (20060101); D06M 15/21 (20060101); B32b
007/04 () |
Field of
Search: |
;161/62,67
;117/69,70,138.5 ;260/453,408,455,556 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: McCamish; Marion E.
Attorney, Agent or Firm: Alexander, Sell, Steldt &
DeLaHunt
Claims
What is claimed is:
1. A pile fabric comprising a backing and pile fibers attached to
said backing at their proximal ends and exposed at their distal
ends, said pile fibers having a first coating consisting
essentially of fluoroaliphatic radical containing component
constituting about 0.05 to 0.2 percent by weight of the pile fiber
weight of said fabric and substantially completely covering their
entire lengths and a second coating consisting essentially of
fluoroaliphatic radical containing component constituting about 0.1
to about 0.4 percent by weight of the pile fiber weight of said
fabric over not more than 25 percent of their length at the exposed
distal ends of said pile fibers, said fabric having enhanced and
durable dry soil resistance and resistance to stain wicking and
penetration.
2. A pile fabric according to claim 1 wherein the second coating
comprises fluoroaliphatic radical free organic adjuvant solid at
20.degree. C. and having a glass transition temperature no lower
than 45.degree. C.
3. A pile fibric according to claim 1 wherein the second coating
comprises ultrafine inorganic adjuvant.
Description
This invention relates to a process for preserving hand or texture
in a piled fabric while at the same time providing dry soil
resistance, stain resistance, cleanability and in certain
embodiments, abrasion resistance.
The treatment of various textile fabrics with fluorochemicals to
impart water and oil repellency has been known to those in the art
for several years. For example, various fluorochemical compounds
have been disclosed previously for use on textile fabrics made from
natural fibers alone, such as wool, cotton, silk, etc., and also
for use on textile fabrics made from natural fibers alone or in
combination with certain synthetic fibers, e.g., nylon, polyester
and rayon. Various fluorochemicals have also frequently been used
in conjunction with crease-resistant resins, hand modifiers, water
repellents and the like to improve fabric performance.
However, treatment with such fluorochemical compounds has not been
useful or practical for all uses and has been especially
impractical for treating fibers and fabrics which are subjected to
severe abrasion and compressive forces as, for example, is normal
with carpets.
Pile fabrics are here considered to include such upholstery fabrics
as corduroy and velvet and pile carpets having loop piles, cut
pile, tip sheared pile, random sheared pile as well as shag, plush
and sculptured piles.
It has been proposed by others, e.g., U.S. Pat. Nos. 3,068,187;
3,256,230; 3,256,231; 3,277,039 and 3,503,915, to mix fluorinated
polymers with non-fluorinated polymers to obtain a mixture (in a
water or solvent solution or dispersion) which will impart good
water and oil repellency to textiles, paper and leather. As
described in those references, by mixing a relatively inexpensive,
non-fluorinated polymer with a fluoroaliphatic radical containing
polymer, one can obtain a relatively inexpensive textile fabric or
fiber treating mixture which will impart water and oil repellency
to the substrate. For economic reasons, those patents suggest using
only a minor proportion of the fluoroaliphatic polymer in the
mixture, i.e., the non-fluorinated polymer is primarily a diluent
in the mixture.
Generally, attempts have been made by others with fluorochemical
treatments to improve dry soil resistance of substrates, but such
treatments are not durable to severe abrasion. Also, treatments
proposed by others which resist abrasion tend to be receptive to
dry soil under conditions of high compressive load. As a result,
all of the prior art treatments satisfactory for apparel or
upholstery fabrics failed to provide traffic-durable soil
resistance, particularly to dry soil, to rugs and carpets.
Generally, resistance to abrasion increases with increasing
treatment level and consequently many prior art treatments
sufficient to provide substantial abrasion resistance tended to
stiffen the pile.
The present invention has as an aim and provides a process for
producing novel soil-resistant pile fabrics and novel processes for
the fluorochemical treatment of fabrics, particularly pile carpets,
to impart durable stain repelling, anti-wicking and soil-resistant
properties thereto. The process of the invention is useful for
various types of pile fabrics such as, for example, those having
fibers of polyester, polyolefin, nylon, acrylic, modacrylic,
acetate (cellulose acetate), rayon (i.e., regenerated cellulose),
polyvinylchloride, wool, cotton, and mixtures thereof.
In accordance with the invention, there is provided a process for
treating pile fabric which comprises two steps. In the first step,
a light coating of a fluorochemical composition is applied to the
entire pile, and, if desired, also to the backing. This coating is
preferably applied by padding, top spraying, roll coating or other
method which will assure complete coverage of the pile fiber
surface at a level of about 0.05 to 0.2 percent by weight of pile
fibers, at least sufficient to prevent wicking of stains through
the pile. The treatment may be applied to the yarn before
converting into a carpet or other fabric. A squeeze roll treatment
after initial application is desirable to assure good penetration
of the treatment into the pile. The fluorochemical material may be
dissolved or dispersed in an aqueous or non-aqueous, i.e., organic,
solvent. The treated fiber or carpet is preferably dried
sufficiently to render the fluorochemical treatment insoluble or at
least so slowly soluble as not to be removed by the following step
or during cleaning operations. It will be recognized by those
skilled in the art that a treatment such as this first step would
be insufficient in itself to provide abrasion and dry soil
resistance as it is at a lower level than would have been used in
one step processes of the prior art. In the process of the
invention, however, this step protects particularly those parts of
the carpet not generally subject to abrasion. It will be seen that
to achieve a level sufficient to confer abrasion resistance to the
entire structure of the carpet would not only result in an
uneconomic use of very large amounts of treating materials but
would also render the pile so stiff as to have an unpleasant hand
and to be almost bristle-like.
The second step also is the application of a fluorochemical
composition, which composition may be the same as used in the first
step, but in the second step the coating is applied preferentially
to the outer or exposed part of the pile so as to be limited
insofar as possible to the outer 25 percent by length or less
thereof. The types of treating solutions used may also be aqueous
or organic dispersions or solutions, although aqueous suspensions
or dispersions are somewhat preferred. Fillers such as finely
divided alumina, silica, and/or other material may be included. The
amount of fluorochemical composition applied in the second step is
about 0.1 to 0.4 percent by weight of the total pile. Inasmuch as
it is restricted to 25 percent or less of the pile length, it will
be evident that the coating over the twice-treated portion is much
heavier and thicker than that which was applied in the first
step.
The process of the invention is not restricted to any particular
fluorochemical treating composition for the first step. A large
number of fluorochemical materials are suitable as will become
apparent from the disclosure herein. They may be polymeric or
non-polymeric and are solid at about 20.degree.-25.degree. C. They
are both water and oil repellent. Adjuvants may be added in either
step for additional benefits including fungicides, bactericides,
mildew preventative, antistatic agents, mothproofing materials and
fiber lubricants. Adjuvants with glass transition temperatures (or
melting points) above 45.degree. C. may be used in proportions up
to 10:1 with respect to fluorochemical and downward to 1:2 if solid
at room temperature with glass transition temperature below
45.degree. C.
In this process non-polymeric and polymeric fluorochemicals useful
for the first step contain from about 15 to 60 percent by weight
fluorine and comprise fluoroaliphatic radicals containing at least
three fluorinated carbon atoms including therein a terminal
CF.sub.3 group. Among polymeric fluorochemicals which may be used,
segmented polymers with fluorine content of about 15 to about 30
percent are particularly useful.
The fluorochemical compositions used for the second step contain
about 15 to 60 percent of fluorine and may be non-polymeric or may
be polymers with molecular weight up to and above about 20,000.
They also combine fluoroaliphatic radicals containing at least
three fluorinated carbon atoms including a terminal CF.sub.3
group.
All the fluorochemicals used in the second step are normally
non-rubbery, non-tacky, solid, water insoluble and preferably free
from ethylenic or acetylenic unsaturation. They should have at
least one major transition temperature (glass temperature or
melting point) above about 45.degree. C. Certain non-polymeric
fluorochemicals as described in U.S. Pat. No. 3,398,182, are noted
as being useful.
The treatment in the second step may further include as adjuvants
fluorine free polymers and hard, very fine particulates such as
inorganic oxides, e.g., alumina, silica, titania, silicates.
Suitable sizes are particularly of the order of 1 micron and
preferably less.
The following examples illustrate the best mode presently
contemplated of practicing the invention. In all cases portions
about 30 .times. 30 cm. are treated. Carpets are: undyed loop pile
nylon carpet (18 ounces/sq. yd, or about 610 g./sq. meter pile
weight), gold loop pile acrylic (about 1,100 g. per sq. meter pile
weight, undyed loop pile random-shear polyester (about 1,200 g. per
sq. meter pile weight) and undyed loop pile random-shear wool
(about 1,200 g. per sq. meter pile weight). Two different
treatments for the first step are employed and a composition for
the second step is coated on the treated carpets and also, at two
different levels, on carpet not subjected to the first step.
First step treatment A employs a 0.1 percent by weight solution in
trichloroethylene of random copolymer of 5 percent by weight methyl
acrylate, 25 percent by weight butyl acrylate and 70 percent of
N-methyl perfluorooctane-sulfonamidoethyl methacrylate (C.sub.8
F.sub.17 SO.sub.2 N(CH.sub.3)C.sub. 2 H.sub.4 OCOC(CH.sub.3
=CH.sub.2). The polymer for treatment A is prepared as follows: A
mixture of 48 parts of C.sub.2 F.sub.3 Cl.sub.3, five parts of
C.sub.2 HCl.sub.3, 17.5 parts C.sub.8 F.sub.17 SO.sub.2
N(CH.sub.3)C.sub.2 H.sub.4 O.sub.2 CC(CH.sub.3)=CH.sub.2 is heated
at 65.degree. C. until solution is complete. The container is then
purged with nitrogen and 0.2 parts of benzoyl peroxide added.
Agitation at 65.degree. C. is continued for 16 hours. A 32 percent
solids solution is obtained. The carpet is padded to 100 percent
wet pickup (55 g. solution for a piece of carpet having 55 g. pile
fiber above the primary backing). After drying, the carpet is cured
at 120.degree. C. for 4 minutes.
Treatment B for the first step employs an aqueous suspension of 0.1
percent by weight of a copolymer of 10 percent by weight butyl
acrylate and 90 percent by weight of
N-methylperfluorooctanesulfonamidoethyl-acrylate (C.sub.8 F.sub.17
SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.4 OCOCH=CH.sub.2) which is padded
on to 100 percent by weight of the top pile fiber and dried and
cured for 5 minutes at 150.degree. C. The suspension is made by
emulsion polymerization at 80.degree. C. under nitrogen (agitating
for 16 hours) of 10 and 90 parts of the comonomers respectively in
240 parts water, 60 parts acetone using 5 parts of a commercial
emulsifier "Ethoquad 18/25" with 0.5 parts 8-dodecyl mercaptan and
0.2 parts potassium peroxydisulfate. Ethoquad 18/25 is a
substituted stearylamine believed to have the formula ##SPC1##
wherein x + y = 25.
Treatment C for the first step employs an aqueous emulsion of 0.1
or 0.2 percent by weight of polymer solids which consist of 90
percent of the copolymer in Treatment B plus 10 percent by weight
of a hybrid copolymer similar to that described in Example 19 of
U.S. Pat. No. 3,574,791, here incorporated by reference.
The treatment for the second step (Treatment Q) is a top spray of
25 percent of the weight of top pile fiber of an aqueous dispersion
containing (weight percentages).
0.4 percent urea
0.4 percent zirconyl chloride
1.0 percent alumina (particle size less than 45 millimicrons)
1.6 percent of reaction product (urethane) 1:1 mole ratio of
tolylene diisocyanate and
N,N-bis(2-hydroxyethyl)perfluorooctanesulfonamide.
The urethane for Treatment Q is prepared as follows:
To a vessel fitted with stirrer, thermometer, condenser and heater
are added 550 parts butyl acetate and 150 parts C.sub.8 F.sub.17
SO.sub.2 N(C.sub.2 H.sub.4 OH).sub.2. The vessel is heated and 200
parts of butyl acetate are distilled to dry the system. The
solution is cooled to 80.degree. C. and 43.5 parts of 2,4-tolylene
diisocyanate and 0.8 parts of triethylene diamine are added.
Reaction is continued with stirring at 90.degree. C. for 16 hours.
The solution is cooled and to it are added 9.7 parts
polyoxyethylene sorbitan monooleate and a solution of 9.7 parts
C.sub.8 F.sub.17 SO.sub.2 NHC.sub.3 H.sub.6 N(CH.sub.3).sub.3 Cl
dissolved in 530 parts of distilled water. The mixture is then
agitated to form a dispersion which is converted to a stable
emulsion by passage through a Manton-Gavlin homogenizer at 175
kg/cm.sup.2. After drying at 70.degree. C., the carpet is cured for
4 minutes at 150.degree. C. Samples are treated first with
Treatments A or B and then with Treatment Q to give Samples AQ and
BQ. Sample Q is a sample of carpet treated solely with Q to give
urethane to 0.4 percent by weight of top pile.
Sample R is obtained by an alternative treatment of untreated
carpet using the same reaction product as for Treatment Q applied
by padding at 100 percent wet pickup from an aqueous dispersion
containing 0.8 percent urethane.
Treatment S for the second step uses the urethane reaction product
of 2 moles of
N,-(2-hydroxy-ethyl)-N-ethylperfluorooctanesulfonamide and 1 mole
of tolylene diisocyanate with 2 parts of polymethylmethacrylate in
aqueous emulsion at levels as indicated below applied either by
spray or padding (as indicated).
Treatments C and S at various levels are used together in the
process of the invention and Treatment S is used alone for purposes
of comparison on carpets of loop pile, nylon, random-shear
polyester, random-shear wool, and random-shear acrylic. In
additions, Treatment S is used as the second step together with
other first steps designated: Treatments D and E.
Treatment D employs the urethane used in Treatment Q at a 0.1
percent level alone and with 0.1 percent colloidal silica.
Treatment E uses emulsions of 0.1 percent of the copolymer of
N-ethylperfluorooctanesulfonamidoethyl methacrylate and isoprene
described below and 0.1 percent of a copolymer of 60 percent
tridecyl acrylate and 40 percent methyl methacrylate. This
treatment is used alone or with 0.2 percent dispersion of
alumina.
The latter copolymer is prepared using 40 g. methylmethacrylate, 60
g. tridecylacrylate in 126 g. water and 54 g. acetone with 3.0 g.
triethyleneglycol mono dodecyl ether (C.sub.12 H.sub.25 O(C.sub.2
H.sub.4 O).sub.3 H), 2.0 g. of emulsifier C.sub.8 F.sub.17 SO.sub.2
NHC.sub.3 H.sub.6 N(CH.sub.3).sub.2.sup.. HCl and 0.2 g. potassium
peroxydisulfate by agitating under nitrogen at 50.degree. C. for 16
hours. The product is an emulsion containing about 35 percent
solids.
The fluorochemical polymer used in Treatment E is prepared as an
emulsion of about 35 percent solids in 144 g. water and 36.0 g.
acetone from 93.5 g. N-ethyl perfluorooctanesulfonamidoethyl
methacrylate, 6.5 g. isoprene, 0.75 g. dodecyl mercaptan, 2.0 g.
C.sub.8 F.sub.17 SO.sub.2 NHC.sub.3 H.sub.6 N(CH.sub.3).sub.2.sup..
HCl, 3.0 g. C.sub.12 H.sub.25 O(C.sub.2 H.sub.4 O).sub.3 H and 0.2
g. potassium peroxydisulfate. Equal portions of the two emulsions
are blended, 8.5 percent ethylene glycol added, and this blend
(about 28-30 percent solids) is then employed in Treatment E to
provide the specified concentrations of polymers.
The blend used in Treatment S is an emulsified urethane and a
dispersion of methyl methacrylate combined to give the desired
concentrations. A solution of 86.5 g. N-(2-hydroxyethyl)-N-ethyl
perfluorooctanesulfonamide and 13.5 g. 2,4-tolylene diisocyanate in
35.5 g. methyl isobutyl ketone catalyzed by 0.05 g. dibutyl tin
dilaurate is heated for about 2 hours at 80.degree. C. and then
emulsified in 73 g. water using 2.5 g. C.sub.8 F.sub.17 SO.sub.2
NHC.sub.3 H.sub.6 N(CH.sub.3).sub.3 C1 and 2.5 g. polyoxyethylene
sorbitan monooleate by twice running through a Manton-Gaulin
homogenizer at 75.degree. C. and 135-160 atmospheres pressure. The
polymethyl methacrylate emulsion is prepared under nitrogen in 100
g. water, 7.5 g cetyldimethylbenzylammonium chloride, 10 g. methyl
methacrylate, 0.2 g. potassium peroxydisulfate, stirred at
50.degree. C. until polymerization starts, and heated to 75.degree.
C. with continuing agitation; 90 g. methyl methacrylate is then
added slowly over about 2 hours. An approximately 45 percent solids
emmulsion is obtained.
Treated carpet samples are subjected to a series of tests in
evaluating the effectiveness of the several treatments in
comparison with one another and with controls:
I. Oil repellency is tested by American Association of Textile
Chemists and Colorists test 118-1966T.
II. Water repellency is tested by placing a few drops of a 70:30
mixture of water: isopropanol on the sample. If the liquid beads
up, the sample passes; if the liquid is absorbed in less than 10
seconds, the sample fails.
III. Stain impact resistance is tested by dropping 3 ml. of a
staining solution, either a blue-dyed aqueous stain or red-dyed
safflower oil from a height of 50 cm. on the sample. If the stain
solution has beaded up and has not wicked out beyond 12 mm. on the
pile fiber next to the primary backing after 1 minute, the test is
passed; otherwise, the sample fails.
IV. Original soil resistance is determined during a walk-on test,
American Association of Textile Chemists and Colorists Test
122-1967T which is rated visually. During about 5 days of daily
rotation and vacuum cleaning, samples are walked on by about 6,000
persons in normal traffic and rated on the scale:
8 -- no visible soil buildup
6 -- slight soil buildup
4 -- much less soil buildup than untreated
2 -- less soil buildup than untreated
0 -- same soil buildup as untreated
Treated samples are shampooed before any soiling using a
commercially available rug shampoo ("Blue Lustre") and a mechanical
shampooing machine to determine stability of the treatment, and
soil resistance is determined by the above walk-on test. Samples
are rated to provide the figures referred to as "Soil after
Shampoo."
V. Stain bloom is determined from samples tested for stain
resistance above by removing the excess staining liquid by blotting
and then cleaning using a commercial paste cleaner ("Texize K-2R")
and thereafter subjecting the sample to walk-on test as above and
rating using the "Deering Milliken Research Corp. Soil Release
Replica" from AATCC Test 130-1969. In this rating system, 1
represents severe blooming, and 5 negligible blooming.
A comparison of Samples AQ, BQ, Q and R with untreated carpet is
given in Table I.
TABLE I ______________________________________ NYLON CARPET
TREATMENTS Sample Oil Water Stain Soil Repel. Repel. Resistance
Resistance ______________________________________ untreated 0 fail
fail 0 AQ 5 pass pass 6 BQ 5 pass pass 6 Q 4 pass fail 6 R 4 pass
pass 3 ______________________________________
It will be seen that Samples Q and R which lack the overall coating
of the first step of the process of the invention are
unsatisfactory in one respect or another.
Carpet samples treated first by padding and squeeze-roll for the
first treatment (C), and then with top-spraying for the second
treatment (S) at the levels indicated are tested for oil and water
repellency before and after walk-on tests as well as for soil
resistance before and after shampooing, stain impact resistance and
stain bloom. In all cases, treated samples passed tests for water
repellency before and after a walk-on test. The results of other
tests are summarized in Table II.
TABLE II
__________________________________________________________________________
Initial Oil Initial Soil Oil Oil Repel- Soil After Stain Repel-
lency Resis- Sham- Bloom Carpet lency After tance poo Treatment
Type Walk-on
__________________________________________________________________________
nylon 6 4 6 5 5 0.2% C polyester 5 1 5 4 5 0.75% S wool 6 1 5 4 5
acrylic 5 2 6 5 5 nylon 5 3 6 5 5 0.1% C polyester 5 1 5 4 5 0.75%
S wool 6 1 5 4 5 acrylic 5 4 6 5 5 nylon 6 3 6 5 5 0.1% C polyester
5 1 5 4 5 0.38% S wool 6 1 5 4 5 acrylic 6 3 5 5 5 0.1% C nylon 6 5
6 5 5 0.25% S* polyester 6 4 5 4 5 with 0.16% colloidal wool 6 1 5
4 5 Al.sub.2 O.sub.3 acrylic 5 5 5 5 5 nylon 0 0 polyester 0 0
untreated wool 0 0 acrylic 0 0
__________________________________________________________________________
S* Using only the urethane moiety of Treatment S, without added
polymethy methacrylate.
Treatments D and E are padded into samples of carpet above and
together with colloidal mineral filler and a second treatment of
Treatment S is top-sprayed. Tests on the samples are summarized in
Table III. All treated samples passed water repellency and oil and
aqueous staining tests except as indicated.
TABLE III
__________________________________________________________________________
Oil Initial Repel- Initial Soil Oil lency Soil After Carpet Repel-
After Resis- Shampoo Treatment Type lency Walk-on tance
__________________________________________________________________________
0.1% D nylon 5 3 6 5 0.75% S acrylic 5 4 5 5 0.1% D nylon 6 5 6 6
plus 0.1% colloidal silica 0.75% S acrylic 5 4 5 5 0.1% E nylon 5 4
6 5 0.75% S acrylic 5 4 4 4 0.1% E plus nylon (a)* 5 4 6 5 0.2%
col- loidal Al.sub.2 O.sub.3 0.75% S acrylic 6 4 3 3
__________________________________________________________________________
(a)* Failed water repellency test after walk-on.
Table IV compares the results of tests similar to those above on
carpets which were treated solely with Treatments S (the second
step of the invention) applied at different levels and by different
methods. Except as indicated by footnotes to the table, c, a and b
respectively, these passed water repellency tests after walk-on and
also oil and aqueous staining tests. All passed water repellency
test initially. It will be seen that a sprayed Treatment S was not
satisfactory as a single step process except at the uneconomically
high levels of 1.5 and 3.0 percent solids on the pile at which
levels, moreover, the carpet was unaccetably harsh and stiff.
TABLE IV
__________________________________________________________________________
Oil Initial Repel- Initial Soil Oil Oil lency Soil After Stain
Carpet Repel- After Resis- Sham- Bloom Treatment Type lency Walk-on
tance poo
__________________________________________________________________________
nylon (a,b) 5 2 6 4 1 polyester 4 1 5 4 2 0.38% S (a,b,c) sprayed
wool (a) 4 1 5 2 2 acrylic (a,b) 5 4 6 5 1 nylon (a,b) 5 3 6 5 1
0.75% S polyester 3 2 5 4 1 sprayed (a,b) wool (a) 5 1 5 4 2
acrylic (a,b) 5 4 6 5 1 nylon 4 1 4 2 5 0.6% S polyester (c) 4 1 5
3 5 padded wool 5 0 5 2 5 acrylic 4 3 4 3 5 nylon 5 3 6 4 5 1.5% S
polyester 5 2 5 4 5 padded wool 6 1 6 4 5 acrylic 5 4 4 4 5 nylon 5
4 6 4 5 3.0% S polyester 5 3 5 4 5 padded wool 6 2 6 5 5 acrylic 5
4 6 5 5 nylon 1 untreated polyester 1 wool 2 acrylic 1
__________________________________________________________________________
a Failed oil staining b Failed aqueous staining c Failed water
repellency after walk-on test
* * * * *