Note: Descriptions are shown in the official language in which they were submitted.
41843 CAN lA
3 7 ~
Description
TREATING FIBROUS POLYAMIDE ARTICLES
The present invention relates to a process for
providing stain resistance to polyamide articles, such as
nylon and wool carpets, nylon, wool, and silk fabrics, and
natural and synthetic leathers.
Fibrous polyamide articles such as nylon and wool
10 carpets, nylon, wool, and silk fabric, natural leather, and
synthetic leathers such as UltrasuedeTM are particularly
susceptible to staining by natural and artificial acid
colorants such as are commonly found in many foods and
beverages. A need has long been felt for processes for
lS economically providing such fibrous polyamide articles with
resistance to staining by acid colorants. Particularly
desirable are processes by which stain resistance can be
imparted to fibrous polyamide articles during conventional
processing and treating operations.
U.S. Patent No. 4,501,591 (Ucci et al.) discloses
a process for providing stain-resistant polyamide carpets
in which a sulfonated phenol-formaldehyde condensation
product and an alkali metal silicate are added to the dye
liquor in a continuous dyeing process, followed by
25 steaming, washing, and drying the carpet.
U.S. Patent No. 4,592,940 (Blyth et al.)
discloses a process for imparting stain resistance to nylon
carpet by immersing the carpet in a boiling aqueous
solution of a selected phenol-formaldehyde condensation
30 product at a pH of 4.5 or less. The process is carried out
in conventional beck dyeing apparatus subsequent to dyeing
(generally at a pH of 6.5 to 8.0) by either acidifying the
bath to pH 4.5 or less or draining the dye bath and then
replacing the dye bath with a corresponding amount of water'
35 adjusted to pH 4.5 or less. Blyth et al. disclose that
insufficient condensation product for imparting stain
~'
~3t3~87~
--2--
resistance is picked up by the carpet at pH greater than
4.5 and temperature less than 95~C.
U.S. Patent No. 4,579,762 (Ucci) discloses'
stain-resistant nylon carpet in which the nylon fibers are
5 made from polymer modified to contain, as an integral part
of its polymer chain, sufficient aromatic sulfonate units
to improve the acid dye resistance of the fibers and in
which the backing adhesive contains a fluorochemical in an
amount sufficient to render the backing a barrier to
10 liquids-
Japanese Examined Patent Application (Kokoku) No.
48-8789 (1973) (Meisei) discloses a method for treatment of
dyed polyamide fibers to improve anti-static and
anti-melting properties and moisture resistance in which a
lS ligand oligomer, formed from sulfonated
4,4'-dihydroxy-diphenyl sulfone-formaldehyde condensate
with a metal compound prepared from citric acid and a metal
chloride, metal oxide, or organic metal salt, is applied to
fiber from a treatment bath or, alternatively, the
20 sulfonated 4,4'-dihydroxy-diphenyl sulfone-formaldehyde
condensate and a metal compound prepared from a metal salt,
citric acid and hydroxy acetic acid, are added to the
treatment bath separately.
U.S. Patent No. 4,329,391'(McAlister) discloses
25 the treatment of synthetic fibers with a sulfonated
polyester stain-releasing finish in an aqueous bath which
includes the addition of water-soluble salts to the aqueous
fabric treating bath. The treatment provides a finish
which enhances oily soil release during after-stain
30 laundering.
U.S. Defensive Publication T949,001 (Pacifici)
discloses a process for improving the durability of
water-dispersible polyester and polyester amide textile
finishes on fabric where the fabric, after application of
35the finish, is treated with an aqueous solution of
polyvalent metal salts.
_3_ ~3~378
U.S. Patent No. 3,322,488 (Feeman) discloses
sulfomethylated condensation products of bisphenols and
aldehydes for use in reserving synthetic polyamide and
polyurethane fibers to render them resistant to acid and
5 direct dyes.
U.S. Patent No. 3,663,157 (Gilgien et al.)
discloses a process for printing nylon fabric with disperse
or monosulfonated acid dyes wherein the fabric is
pretreated with an aqueous solution of a fiber-substantive,
10 water-soluble, anionic resist which is a polycondensate of
a diarylsulfone containing at least one phenolic hydroxy
group with formaldehyde.
U.S. Patent No. 3,926,548 (Moriyama et al.)
discloses aminated hydrophobic fibers having a surface
15 resistant to anionic dyes, the surface of the fibers having
been treated with a compound having groups capable of
linking to amino groups in the fibers to form covalent
bonds. Such groups include halotriazinyl, halopyrimidinyl,
haloquinoxalyl, haloacrylamido, vinylsulfo groups, etc., or
20 any other groups that can produce these groups. Also
suitable are compounds having anionic groups, for example,
sulfonate, carboxylate, sulfate, phosphate groups, etc.,
besides the highly reactive groups capable of reacting with
amino groups.
U.S. Patent No. 3,959,559 (Kimoto et al.)
discloses a process for producing modified synthetic fibers
in which the fibers are treated with a reaction product of
a specified s-triazine or piperazine derivative, with a
specified derivative of polyoxyethylene and further
30adhering onto the resulting fibers a specified aromatic
sulfonic acid. The modified fibers resist contamination
from liberated dyestuff or ionic contaminants during
laundering or dry cleaning.
U.S. Patent No. 4,322,512 (Lenox) discloses
35treating a polyamide textile material with a substituted
trimellitic anhydride compound, the treatment decreasing
the textile material's affinity for acid dyes.
_4_ ~39$7~
U.S. Patent No. 4,343,923 (Lenox et al.)
discloses a method for decreasing a textile material's
affinity for acid dyes in which the textile material is
pretreated with an acylimidazole compound.
Brownewell, Ralph G., "Two New Chemicals Create
Better Multicolored Nylons," American Dyestuff Reporter,
Vol. 68, No. 3, 1979, pp 38-41, discloses processes for
providing nylon fabrics which are resistant to coloration
by acid dyes by treatment with SandospaceTM S, a product of
Sandoz Colors and Chemicals, believed to be a benzenoid
triazine derivative.
U.S. Patent No. 4,563,190 (Topfl) discloses a
dyeing assistant useful in the dyeing of polyamide fibers
with acid dyes. The dyeing assistant is a mixture of (A) a
sulfonated condensation product of hydroxyaryl compounds
and formaldehyde or a sulfonated N-aryl-melamine
derivative, and (s) a specified quaternary ammonium, and,
optionally, (C) a siloxane/oxyalkylene copolymer and (D) a
polar solvent.
European Patent Publication No. 0,102,690
discloses increased exhaustion of fluorochemical treating
agents for providing oil and water repellency by the
addition of salt compounds such as sodium sulfate and
citrate, magnesium chloride, ammonium sulfate and chloride,
aluminum sulfate, calcium chloride, and potassium chloride.
U.S. Patent No. 4,013,627 (Temple) discloses a
fluorochemical polymer for treating fabrics to provide oil
and water repellency, the polymer being derived from
fluorochemical acrylate monomer, a vinyl monomer free of
non-vinylic fluorine, and a vinyl monomer which contains an
onium ionic group. Salts, such as alkali metal sulfates
and low molecular weight alkylamine hydrochlorides, may be
added, as adjuvants, to textile treating baths containing
the fluorochemical polymer to aid deposition of the polymer
onto the fabric being treated.
European Patent Publication No. 0,016,658
(Monsanto) discloses soil-resistant carpet yarns prepared
.
-5- ~3~87~
by coating the yarn with a soil retardant agent such as a
fluorochemical and a retaining agent such as zirconium
oxide.
The present invention provides a method for
5 providing fibrous polyamide material with stain resistance
to natural and artificial acid colorants comprising
contacting the fibrous polyamide material with an aqueous
solution comprising a normally solid, water-soluble,
partially sulfonated novolak resin, which comprises the
10 condensation product of at least one phenolic compound and
an aldehyde such as, for example, formaldehyde or
acetaldehyde, and a water-soluble divalent metal salt. The
resin and salt are applied in sufficient amounts and for
sufficient time at a given temperature to provide stain
15 resistance. The combination of the sulfonated novolak
resin and divalent metal salt provides surprising effective
stain resistance using reduced amounts of the resin and
permits application over a wide pH range.
The method of this invention can be carried out
20in three different ways. One method comprises the steps of
Ia) adding to a dyebath, before, during, or after
dyeing of the fibrous polyamide material, such as in a dye
beck with nylon carpet, at least 0.1% solids based on the
weight of the fabric (owf) of the sulfonated novolak resin
25and at least 1% owf of the divalent metal salt,
Ib) immersing the polyamide material in the
dyebath for a time and temperature sufficient to exhaust
the sulfonated novolak resin onto the polyamide material,
Ic) removing the treated polyamide material from
30the dyebath, and
Id) drying the removed polyamide material.
A second method comprises the steps of
IIa) applying to the polyamide material an aqueous
solution comprising at least 0.1% solids owf of the
35sulfonated novolak resin and at least 1% owf of the
divalent metal salt, such as during continuous dyeing of
nylon carpet using KusterTM or OttingTM continuous dyeing
equipment,
6 i~878
IIb) steaming the treated polyamide material for a
time sufficient to effect adherence of the sulfonated
novolak resin to the polyamide material, and
IIc) drying the polyamide material.
A third method comprises the steps of
IIIa) padding an aqueous solution comprising at
least 0.1% owf of the sulfonated novolak resin and at least
1% owf of the divalent metal salt onto the polyamide
material and
IIIb) drying the polyamide material.
The invention further provides including a
fluorochemical composition in the aqueous solution
comprising the sulfonated novolak resin and the divalent
salt in step Ia, IIa, or IIIa to provide the polyamide
15 material with oil and water repellency. The invention
further provides an aqueous solution useful in providing
stain resistance to fibrous polyamide material comprising
the water-soluble partially sulfonated novolak resin and
the water-soluble divalent salt. The invention also
20 provides fibrous polyamide materials such as nylon, silk,
and wool fabrics, yarns, and fibers, nylon and wool
carpets, and natural and synthetic leather such as
UltrasuedeTM with stain resistance by treating the
- polyamide materials as described in method I, II, or III
25hereinabove.
The present invention still further provides
fibrous polyamide materials with stain resistance and oil
and water repellency by treating the polyamide material, as
described in method I, II, or III hereinabove, with a
30fluorochemical composition added to the treating solution.
The sulfonated novolak resins useful in this
invention include known substances such as those
compositions which are condensation products of
formaldehyde with bis(hydroxyphenyl)sulfone and
35phenylsulfonic acid. Instead of, or in addition to,
formaldehyde, another aldehyde such as, for example,
acetaldehyde, furfuraldehyde, or benzaldehyde, can be used
to make the condensation product. Also, other phenolic
_7~ 9878
compounds such as, for example, bis(hydroxyphenyl)alkane,
e.g., 2,2-bis(hydroxyphenyl)propane, and bis(hydroxyphenyl)
ether compounds can be used instead of, or in addition to
the bis(hydroxyphenyl)sulfone. The sulfonated novolak
resin is partially sulfonated, i.e., has a sulfonic acid
equivalent weight of about 300-1200, preferably 400-900.
Examples of such resins are disclosed in U.S. Patent No.
4,592,940 (Blyth et al.). Also commercially available
sulfonated novolak products are available such as
IntratexTM N, available from Crompton and Knowles Corp.,
and ErionalTM PA, available from Ciba-Geigy Corp.,
NylofixanTMP available from Sandoz Ltd. Mesitol NBS,
available from Mobay Chemical Corp., Resist #4, available
from Lyndal Chemical Co., AmeriolateTM, available from
American Emulsions Co. Inc. and SynthabondTM 1938 available
from Piedmont Chemical Industries. Sulfonation of phenolic
compounds is taught, for example, in Sulfonated and Related
Reactions, E. E. Gilbert, Interscience Publishers, (1965).
Condensation of phenol-formaldehyde resins is taught, for
example, in Phenolic Resins, A. Knop et al.,
Springer-Verlag, (1985).
The divalent metal salts useful in the present
invention include water soluble inorganic and organic salts
of metals such as magnesium, barium, calcium, and zinc.
Inorganic metal salts include chlorides, sulfates, and
nitrates of these metals. Organic metal salts include
acetates and formates of these metals. Preferred divalent
metal salts are magnesium sulfate, magnesium chloride and
magnesium acetate. Mixtures of two or more salts can also
be used in this invention. Generally, when both the
sulfonated novolak resin and fluorochemical compositions
are in the aqueous treating solution, magnesium salts are
preferably used to achieve both stain resistance and oil
and water repellency.
The fluorochemical compositions useful in the
present invention for providing oil and water repellency
J~
7 ~
--8--
include anionic, cationic, or nonionic fluorochemicals such
as the fluorochemical allophanates disclosed in U.S. Patent
No. 4,606,737 (Stern); fluorochemical polyacrylates
disclosed in U.S. Patent Nos. 3,574,791 (Sherman et al.)
5 and 4,147,851 (Raynolds); fluorochemical urethanes
disclosed in U.S. Patent No. 3,398,182 (Guenthner et al.);
fluorochemical carbodiimides disclosed in U.S. Patent No.
4,024,178 (Landucci); fluorochemical guanidines disclosed
in U.S. Patent No. 4,540,497 (Chang et al.).
The sulfonated novolak resins are preferably used
in an amount of at least 0.1% solids owf, more preferably
0.15% owf, most preferably at least 0.35% owf. Amounts in
excess of 3% owf generally do not provide any appreciable
increase in stain resistance. The amount of sulfonated
15 novolak resin required to provide adequate stain resistance
depends on the fibrous polyamide material being treated.
For example, nylon 6 and wool generally require larger
amounts of the resin than nylon 66. When the polyamide
material is heat-set carpet yarn, yarn heat-set under moist
20conditions, e.g.J in an autoclave, generally requires
larger amounts of the resin than with yarn heat-set under
substantially dry conditions.
The divalent metal salts are preferably used in
an amount of at least 1% owf, more preferably at least
251.5% solids owf, most preferably at least 2% solids.
Amounts of the salt in excess of 5% owf generally do not
provide any appreciable increase in stain resistance.
The fluorochemical composition, when included in
the treating solution, is preferably present in an amount
30Of at least about 0.15% solids owf, more preferably at
least 0.2% solids owf, most preferably 0.35% owf.
Generally, amounts of the fluorochemical composition in
excess of 2% solids owf do not appreciably improve the oil
and water repellency. Generally, when the polyamide
35material is nylon fiber, smaller denier fiber requires
larger amounts of the fluorochemical composition than
larger denier fiber.
9 ~3~8~
The sulfonated novolak resin and water-soluble
divalent metal salt can be applied from an aqueous exhaust
bath such as is used in beck dyeing of carpet. The
sulfonated novolak resin and the water soluble divalent
5 metal salt can be added to the aqueous dye bath solution
and exhausted concurrently with the dye. Generally, the
dye bath is maintained at a temperature at or near the
boiling point for a period of 10 to 90 minutes or more to
effect exhaustion of the dye and the sulfonated novolak
10 resin. Surprisingly, the dye bath can be maintained in the
normal pH range of 4.5 to 8.0 with excellent results. Dye
bath pH can range from 2.0 to 12.0, although pH in the
range of 4 to 7 is preferred.
Alternatively, the sulfonated novolak resin and
15 the water-soluble divalent metal salt can be added to the
aqueous dye bath after exhaustion of the dye or the dyebath
can be drained and fresh water added prior to the addition
of the sulfonated novolak resin and the water-soluble
divalent metal salt. Generally, the resin/salt bath is
20 maintained at a temperature at or near boiling for a period
of time sufficient to exhaust the resin, usually 10 to 90
minutes.
The sulfonated novolak resin and divalent metal
salt can be applied during continuous dyeing, such as with
25RusterTM or OttingTM carpet dyeing equipment. The
sulfonated novolak resin and the water-soluble divalent
metal salt can be added directly to the aqueous dye
solution and the solution is conventionally applied to the
polyamide carpet. Alternatively, the sulfonated novolak
30resin and the water-soluble metal salt can be applied
during a wetting out step prior to application of the dye.
The carpet is then steamed, as usual, for 3 to 5 minutes.
The sulfonated novolak resin and divalent salt
can also be applied to polyamide material by a padding
350peration. This can be done as a separate step or in
conjunction with the application of various convention
finishes such as wetting agents, softeners, and leveling
7 ~
--10--
agents. After application of the resin/salt solution, the
polyamide material is conventionally dried.
Fluorochemical compositions for providing oil and
water repellency can also be applied in conjunction with
5 the sulfonated novolak resin. The fluorochemical
composition is simply added in an appropriate amount to the
treating solution. In some cases, particularly in exhaust
applications, useful divalent metal salts may be limited to
the inorganic and organic magnesium salts.
The following non-limiting examples serve to
illustrate the invention. In the following examples, all
ratios are by weight and percentages are weight percent
unless otherwise indicated. In the examples where the
material being treated is nylon 66 carpet, the carpet is
15 scoured, greige, unbacked, level-loop carpet.
Preparation of a sulfonated phenol-formaldehyde resin
(hereinafter SPFR):
To a three-neck flask, fitted with a mechanical
stirrer, thermometer, and condenser, was added 473 g of
acetic anhydride and 945 g of 4,4'-dihydroxydiphenyl-
sulfone (DDS). Then 473-g of conc. sulfuric acid was added
via a dropping funnel over a period of one hour with
25stirring. The resulting reaction mixture was heated and
stirred at 100~C for 7 hours. Water (340 g) was added in
portions while distilling off acetic acid over one hour.
After addition of 250 g of 37% aqueous formaldehyde and
338 g of water, the reaction mixture was heated to 100~C
30for 6 hours. The resulting sulfonated 4,4'-dihydroxy-
diphenylsulfone-formaldehyde condensate was diluted with
1400 g of water and neutralized to a pH of 6.0 with 550 g
of 5% NaOH to yield the sodium salt of the partially
sulfonated novolak resin product as a 36% aqueous
35concentrate (SPFR).
--1 1--
In the following examples, fibrous polyamide
materials were evaluated using the following test methods:
Stain Resistance (SR)
A 1 g sample of the fibrous polyamide material
under evaluation is placed in 40 ml aqueous solution
containing 0.008 weight percent FD~C Red Dye No. 40 and
0.04 weight percent citric acid at room temperature (22~C)
and agitated for one hour. The sample is removed from the
10 dye solution, rinsed and blotted with paper towels to
remove excess moisture. The amount of staining is
evaluated visually using a rating scale which ranges from
1-5, where 1 is essentially unstained and 5 is heavily
stained. Generally, a stain resistance of less than 3 is
15 satisfactory.
Water Repellency (WR)
The water repellency of treated polyamide samples
is measured using a water/isopropyl alcohol test, and is
20 expressed in terms of a water repellency rating on a scale
of 0 to 10 of the treated carpet or fabric. Treated
carpets which are penetrated by or resistant only to a 100
percent water/0 percent isopropyl alcohol mixture (the
least penetrating of the test mixtures) are given a rating
25Of 0, whereas treated fabrics resistant to a 0 percent
water/100 percent isopropyl alcohol mixture (the most
penetrating of the test mixtures) are given a rating of 10.
Other intermediate values are determined by use of other
water/isopropyl alcohol mixtures, in which the percentage
30amounts of water and isopropyl alcohol are each multiples
of 10. The water repellency rating corresponds to the most
penetrating mixture which does not penetrate or wet the
fabric after 10 seconds contact. In general, a water
repellency rating of at least 1, is desirable for carpet.
8 7 ~
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Oil Repellency (OR)
The oil repellency of the treated polyamide
samples is measured by AATCC Standard Test 188-1978, which
test is based on the resistance of treated fabric to
5 penetration by oils of varying surface tensions. Treated
fabrics resistant only to NujolTM, a brand of mineral oil
and the least penetrating of the test oils, are given a
rating of 1, whereas treated fabrics resistant to heptane
(the most penetrating of the test oils) are given a value
10 of 8. Other intermediate values are determined by use of
other pure oils or mixtures of oils. The rated oil
repellency corresponds to the most penetrating oil (or
mixture of oils) which does not penetrate or wet the fabric
after 10 seconds contact rather than the 30 seconds contact
15 of the Standard Test. Higher numbers indicate better oil
repellency. Additionally, a value of 0 indicates no
resistance to NujolTM. In general, an oil repellency of at
least 1 or greater is desirable for carpet.
Examples- 1-3 and Comparative Example C1-C4
Samples of nylon 66 carpet which had been
heat-set for 10 minutes at 150~C under substantially dry
conditions, were immersed in an aqueous bath containing
0.3% solids SPFR and the amount of various salts shown in
25Table 1. A 20:1 liquor to fabric ratio, a pH of 6 a bath
temperature of 97~C, and a treatment time of 90 minutes
were used. The carpet samples were removed from the bath,
rinsed, and dried for 10 minutes at 70~C and then for 5
minutes at 130~C. The carpet samples, together with a
30carpet sample to which no SPFR and no salt were added
(Comparative Example C1), were tested for stain resistance
(SR). The results are shown in Table 1.
13~9~7~
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Table 1
Salt Salt amount
Example ~y~ (% owf) SR
C1 none none 5
1 MgCl2 1 1.5
2 MgSO4 1 1.5
3 Mg(OOCCH3) 2 1 1.5
C2 (NH4 )2 SO4 1 4.5
C3 (NH4)2SO4 5 3.0
C4 NaCl 5 3.0
As can be seen from the data in Table 1, the use
of divalent magnesium salts provides significantly better
stain resistance to the carpet than does the use of the
monovalent salts, ammonium sulfate and sodium chloride,
even when relatively large amounts (5% owf) of the
monovalent salts are used.
Examples 4-8 and Comparative Examples C5-C9
In Examples 4-7, samples of nylon 66 carpet which
had been heat-set for 10 minutes at 150~C under
substantially dry conditions, were immersed for 90 minutes
in an aqueous solution at 97~C and a pH of 6 and a liquor
to fabric ratio of 20:1 using 0.2% owf SPFR with 2% solids
owf of various salts. In Comparative Example C5, no SPFR
or salt were used and, in Comparative Example C6, SPFR was
used without salt. In Example 8 and Comparative Examples
C7-C9, 0.25% owf of a fluorochemical oil and water
repellent composition, FX-364TM, available from 3M Company,
was added to the treating solution containing SPFR and
salt. Each sample was removed from the solution, rinsed,
and dried for 10 minutes at 70~C and then for 5 minutes at
130~C. Each sample was tested for stain resistance ( SR),
oil repellency (OR), and water repellency (WR). The
results are shown in Table 2.
~,
-14- ~ ~ ~g~7g
Table 2
Example SPFR Salt FC SR ORc wRc
C5 a _ _ 5 F F
C6 xb - - 4-5-5 F F
4 x MgCl2 - 1. 5 F F
x BaCl2 - 1. 5-2 F F
6 x CaCl2 - 1. 5-2 F F
7 x znCl2 - 1.5-2 F F
- 10 8 x MgCl2 x 1. 5 4 4
C7 x BaCl2 x 5 F 0
C8 x CaCl2 x 4. 5-5 4 3
C9 x znCl2 x 4 5 4
a) a dash indicates the constituent is not present
b) "x" indicates the constituent is present
c) ~F~ means the sample fails test, i.e., worse than 0
As can be seen from the results in Table 2, each
of the samples treated with SPFR have good stain resistance
when used with the indicated divalent metal salts although
very little stain resistance resulted from the SPFR alone
at this concentration. When the fluorochemical was added,
oil and water repellency were achieved when MgCl2, CaCl2,
and ZnCl2 were present and adequate stain resistance was
achieved only with MgCl2 ~Example 8).
Examples 9-10 and Comparative Examples C10-C11
Samples of nylon carpet which had been heat-set
for 10 minutes at 150~C under substantially dry conditions,
were dyed by immersion in an aqueous bath using 0. 25% owf
TectilonTM slue 5GS~ available from Ciba-Geigy Corp.,
without SPFR~ with 0.15% solids owf SPFR only added, and
with 0.15% solids owf SPFR and 2% owf MgCl2 added. In
Comparative Example C6 only water was used. In each, a
liquor to fabric ratio of 20:1, a bath temperature of 97~C,
a pH of 6 and a treatment time of 90 minutes were used.
-15~ 9 ~ 7 ~
The dye exhausted well in each example to provide a level
blue shade. Each sample was removed from the bath, rinsed,
and dried for 10 minutes at 70~C and then 5 minutes at
130~C. Each sample was evaluated for stain resistance
(SR). The aqueous dye bath constituents and stain
resistance are shown in Table 3.
Table 3
Example ~y~ SPFR ~ 2 SR
C6 - - - 5
C7 x - - 5.0
9 x x - 3.0
x x x 1.0
As can be seen in Table 3, only when both the
SPFR and MgCl2 were present was excellent stain resistance
achieved at this concentration of SPFR.
Examples 11 and 12 and Comparative Examples C12-C16
Samples of wool gabardine fabric were immersed in
an aqueous solution of SPFR and 2.0% owf magnesium acetate
as set forth in Table 4. For each sample, a liquor to
fabric ratio of 20:1, treatment temperature of 97~C, a pH
of about 6 and a treatment time of 90 minutes were used.
Each sample was removed from the treating solution, rinsed,
and dried for 10 minutes at 70~C and then for 5 minutes at
130~C. Each sample was tested for stain resistance (SR).
The results are shown in Table 4.
Table 4
Example SPFR Mg(OOCCH3) 2 SR
C12
C13 0.15 - 5
C14 0.15 x 3
C15 0.30 - 5
11 0.30 x 2
C16 0.50 - 5
12 0.50 x 1.5
~3987~
-16-
As can be seen from the results in Table 4, good stain
resistance is achieved on wool gabardine at SPFR
concentration of 0.30% owf and above when magnesium acetate
was present. No stain resistance was shown when the salt
was not used.
Examples 13-14 and Comparative Examples C17-C18
Samples of chamois (natural leather) and
upholstery-weight, nylon UltrasuedeTM (synthetic leather~
were treated by immersing the sample in water or in aqueous
solutions containing 0.35% solids owf SPFR and 2% owf
magnesium acetate at room temperature at a liquor to fabric
ratio of 20:1 for 46 hours. Each sample was removed from
the treating solution, rinsed and dried for 10 minutes at
70~C and then for 5 minutes at 130~C. Each sample was
tested for stain resistance ( SR), the results are set forth
in Table 5.
Table 5
20Example Material SPFR Mg(ooccH3)2 SR
C17 chamois - - 5
13 chamois x x
C18 UltrasuedeTM - - 4
14 UltrasuedeTM x x
As can be seen from the data in Table 5,
excellent stain resistance can be achieved with both
natural and synthetic leather when both SPFR and salt are
present in the treatment bath.
Examples 15-24 and Comparative Examples C18-C29
Samples of nylon 66 level loop carpet which had
been heat-set for 10 minutes at 150~C under substantially
dry conditions, were dyed by immersing the samples in
aqueous solutions at various pH's using 0.35% solids owf
SPFR with and without 2% owf magnesium acetate at a liquor
to fabric ratio of 20:1, a treatment temperature of 97~C, a
1~3~33'~
-17-
pH of about 6 and a treatment time of 90 minutes in a
LaunderometerTM. A sample also was treated with water
only. Each sample was removed from the treating solution,
rinsed, and dried for 10 minutes at 70~C and then for 5
minutes at 130~C. Each sample was tested for stain
resistance (SR). The results are shown in Table 6.
Table 6
Example ~ SPFR Salt SR
C19 _ 5
C20 3 x - 1.5
3 x x
C21 4 x - 1.5
16 4 x x
C22 5 x - 2.0
17 5 x x 1-1.5
C23 6 x - 2.5
18 6 x x 1.5-2
C24 7 x - 4.5
19 7 x x 1.5
C25 8 x - 5.0
8 x x 1.5-2
C26 9 x - 5.0
21 9 x x 2.5
C27 10 x - 5.0
22 10 x x 2.5-3
C28 11 x - 5.0
23 11 x x 3-3.5
C29 12 x - 5.0
24 12 x x 3
a) Adjusted with acetic acid or sodium hydroxide
solution as required to achieve the desired pH.
The data in Table 6 show that the good stain
resistance obtained with SPFR at pH values of 3-6 is
~4~
18 1 3 s3 ~ ~Q3 ~ ~3
improved by the addition of magnesium acetate. At pH
values of 7-10, the poor stain resistance seen with the use
of only SPFR is improved to acceptable stain resistance
ratings with the addition of magnesium acetate.
Examples 25-27 and Comparative Examples C30-C32
In these Examples, nylon upholstery fabric which
had been heat-set for 10 minutes at 150~ under
substantially dry conditions, was treated by padding (50%
wet pick up) an aqueous solution containing 0.3% solids owf
SPFR with and without 2% owf magnesium chloride salt, and
with and without a 0.3% solids owf of a blend of
fluorochemical oil and water repellent composition,
FC-214TM, available from 3M Company (FC). Each sample was
dried for 10 minutes at 70~C and then for 5 minutes at
130~C. Each sample was tested for stain resistance (SR),
oil repellency (OR), and water repellency (WR). The
results are shown in Table 7.
Table 7
Example SPFR~Y~2 FC SR OR WR
C30 - - - 5 F F
C31 x - - 1.5 F F
x - x 1.5 4 3
26 x x - 1.5 F F
27 x x x 1-1.5 2
C32 - x x 5 5 8
As can be seen from the data in Table 7, when
the magnesium chloride salt was present with the SPFR and
the fluorochemical composition, acceptable oil and water
repellency (rating of at least 1) and improved stain
resistance (rating of 1-1.5) where achieved.
*~ .~
~''
3937~
--19--
Examples 28-42 and Comparative Examples C33-C48
In these examples, samples of nylon 66 level loop
carpet which had been heat-set under substantially dry
conditions for 1 minute at 200~C, were treated by immersion
in an aqueous bath at a liquor to fabric ratio of 21. 5:1,
at treating temperature of 97~C, and a treatment time of 90
minutes with 0. 3% solids owf SPFR various commercial
novolak resins (NR) with and without 2% owf magnesium
chloride and with and without 0.25~ solids owf of a
fluorochemical composition, FX-364, available from 3M
Company ( FC). The pH was adjusted to 3. 5 with acetic acid.
The samples were removed from the treating solution,
rinsed, and dried for 10 minutes at 70~C and then for 5
minutes at 130~C. The samples were tested for stain
resistane (SR), oil repellency (OR), and water repellency
(WR). The results are shown in Table 8.
Table 8
Example NR Salt FC SR ORb WRb
C33 - - - 5 nt nt
C34 A - - 1. 5 nt nt
28 A - - 1. 5 nt nt
C35 B - - 2-2. 5 nt nt
29 B X - 1 nt nt
C36 B - x 2 F
B x x 2. 5 4 7
C37 C - - 1.5-2 nt nt
31 C x - 1 nt nt
C38 C - x 1.5 F O
32 C x x 1 3 6
C39 D - - 1-1.5 nt nt
33 D x - 1 nt nt
C40 D - x 1.5 F O
34 ~ x x 1 4 6
C41 E - - 1. 5 nt nt
E x - 1-1.5 nt nt
-20- 133~8~8
Table 8 ( cont.)
Example NRa Salt FC SR ORb WRb
C42 E - x 1.5 F O
536 E x x 1 - 1.5 F O
C43 F - - 2 nt nt
37 F x - 1 nt nt
C44 F - x 2-2.5 F
38 F x x 1 3 6
0C45 G - - 1 nt nt
39 G x - 1 nt nt
C46 G - x 1 F 2
G x x 1 4 6
C47 H - - 2.5 nt nt
1541 H _ x 1 nt nt
C48 H - x 2.5-3 F 2
42 H x x 1 3 6
a. Novolak resin:
20A) SPFR
B) MESITOL M NBS
C) INTRATEX N
D) ERIONAL PA
E) RESIST #4
F) SYNTHABOND 1938
TM
G) AMERIOLATE
H) NYLOFIXAN P
b. "nt" indicates the sample was not tested
Examples 43-48 and Comparative Examples C49-C51
Samples of nylon 66 level loop carpet which had
been heat-set under substantially dry conditions for 10
minutes at 150~C, were treated by immersion in an aqueous
solution containing 0.5% solids owf SPFR, with and without
35 20% owf magnesium sulfate salt, with and without 0. 5~
solids owf fluorochemical oil and water repellent (FC), and
with and without TectilonTM Blue 5GS dye, available from
~33~7~
-21-
Ciba-Geigy Corp., as indicated in Table 9. Treatment was
carried out at a pH of 4.5, a liquor to fabric ratio of
20:1, a treatment temperature of 97~C, and a treatment time
of 90 minutes. Comparative Example C49 was prepared using
no SPFR, salt, fluorochemical, or dye. Each sample was
removed from the treating solution, rinsed and dried at
70~C for 10 minutes then at 130~C for 5 minutes. Each
sample was tested for stain resistance (SR), oil repellency
(OR) and water repellency (WR). The results are shown in
Table 9.
Table 9
Dye conc.
Example Salt FCa (% owf) SR OR WR
C49 - - - 5 F O
43 x 1 - 1 6 8
44 x 2 - 1 5 6
x 1 0.5 1 6 9
46 x 2 0.5 1 5 7
47 x 1 4 1 5 8
48 x 2 4 1 5 5
C50 - 1 4 1 F O
C51 - 2 4 1 F O
a) fluorochemical 1 is FC-232TM, a cationic fluorochemical
composition available from 3M Company, fluorochemical 2
is FX-364TM, an anionic fluorochemical composition
available from 3M Company.
As can be seen from Table 9, excellent stain
resistance and oil and water repellency are achieved only
when the salt is present as in Examples 43-48. Each dyed
sample was levelly dyed to the expected depth based on the
amount of dye present.
~335378
-22-
Example 49 and Comparative Examples C52-C53
Samples of nylon 66 level loop carpet which had
been heat-set under substantially dry conditions for 1
minute at 200~C, were laboratory dyed using a procedure
which simulates continuous carpet dyeing. Dye formulations
containing 0.5 g/l Karawet M DOSS, available from Lyndal
Chemical Co., 0.25 g/l SequesterentTM 220, available from
Ciba-Geigy Corp., 0.1 g/l sodium thiosulfate, 0.026 g/l
Tectilon Blue 4R200, 0.032 g/l TectilonTM Red 2B200, and
0.050 g/l TectilonTM Orange 3G200, each dye available from
Ciba-Geigy Corp., with and without 0.35% solids owf SPFR
and with and without 2% owf magnesium chloride were applied
to the samples by pressing the samples face down in a tray
containing the dye solution after the samples were wet-out
with a 2 g/l aqueous solution of KarawetTM DOSS. The dye
bath pH was 6Ø The carpet was removed from the dye bath
and steamed at 100~C, 100% r.h. for 5 minutes, dried for 20
minutes at 70~C. and set at 130~C for 10 minutes. The
samples were tested for stain resistance. The results are
shown in Table 10.
Table 10
Example SFPR Salt SR
C52 _ _ 5
C53 x - 4.5
49 x x
The results in Table 10 show that only when the
salt is present, is excellent stain resistance achieved.
Various modifications and alterations of this
invention will be apparent to those skilled in the art
without departing from the scope and spirit of this
invention and this invention should not be restricted to
that set forth herein for illustrative purposes.
