[0001] 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.
[0002] Fibrous polyamide articles such as nylon and wool carpets, nylon, wool, and silk
fabric, natural leather, and synthetic leathers such as Ultrasuede™ 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 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.
[0003] U-S-A-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 steaming, washing, and drying the carpet.
[0004] US-A-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 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 adjusted
to pH 4.5 or less. Blyth et al. disclose that insufficient condensation product for
imparting stain resistance is picked up by the carpet at pH greater than 4.5 and temperature
less than 95°C.
[0005] US-A-4,579,762 (Ucci) discloses stain-resistant nylon carpet in which the nylon fibers
are 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 liquids.
[0006] 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 ligand oligomer, formed from sulfonated
4,4ʹ-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 sulfonated 4,4ʹ-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.
[0007] US-A-4,329,391 (McAlister) discloses 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 laundering.
[0008] 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 the finish, is treated with an aqueous
solution of polyvalent metal salts.
[0009] US-A-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 direct dyes.
[0010] US-A-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, water-soluble, anionic resist which is a polycondensate
of a diarylsulfone containing at least one phenolic hydroxy group with formaldehyde.
[0011] US-A-3,926,548 (Moriyama et al.) discloses aminated hydrophobic fibers having a surface
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 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.
[0012] US-A-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
adhering 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.
[0013] US-A-4,322,512 (Lenox) discloses treating a polyamide textile material with a substituted
trimellitic anhydride compound, the treatment decreasing the textile material's affinity
for acid dyes.
[0014] US-A-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.
[0015] 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 Sandospace S, a product
of Sandoz Colors and Chemicals, believed to be a benzenoid triazine derivative.
[0016] US-A-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 (B) a specified quaternary ammonium, and, optionally, (C) a siloxane/oxyalkylene
copolymer and (D) a polar solvent.
[0017] EP-A-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.
[0018] US-A-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.
[0019] EP-A-0,016,658 (Monsanto) discloses soil-resistant carpet yarns prepared by coating
the yarn with a soil retardant agent such as a fluorochemical and a retaining agent
such as zirconium oxide.
[0020] U.S. Patent No. 4,592,940 (Blyth et al.) discloses nylon carpets which are rendered
resistant to staining normally caused by artificial colorants such as F,D&C Red Dye
No. 40 by immersing the carpets ion a boiling aqueous solution of a selected phenol-formaldehyde
condensation product at a pH of 4.5 or less. A particularly useful condensation product
reported is that obtained by the condensation of formaldehyde with a mixture of diphenolsulfone
and phenolsulfonic acid.
[0021] Japanese Kokai No. 52[1977]-155300 (Kuraray) discloses a composition for flameproofing
synthetic fabrics, such as nylon and polyester, having as a major component prepared
by bonding a compound represented by the general formula
![](https://data.epo.org/publication-server/image?imagePath=1993/10/DOC/EPNWB1/EP87308464NWB1/imgb0001)
(wherein X is COOH or SO₃H or salts thereof and Y is COOH SO3H, H or a group which
is inactive to methlolconversion reaction) and formaldehyde which component has a
methylol conversion degree of 1 to 3 and a degree of number average polymerization
of 1 to 2.
[0022] The present invention provides a method for 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 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 other
than that of a phenol/aldehyde condensation product are applied in sufficient amounts
and for sufficient time at a given temperature to provide stain 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.
[0023] The method of this invention can be carried out in 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 and 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 the dyebath, and
Id) drying the removed polyamide material.
[0024] 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 sulfonated novolak resin and at least 1% owf of the divalent metal
salt, such as during continuous dyeing of nylon carpet using Kuster™ or Otting™ continuous
dyeing equipment,
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.
[0025] 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.
[0026] 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 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 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 Ultrasuede™ with stain resistance
by treating the polyamide materials as described in method I, II, or III hereinabove.
[0027] 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 fluorochemical composition added to the
treating solution.
[0028] 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 phenylsulfonic 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 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.) which is incorporated herein by reference
for this purpose. Also commercially available sulfonated novolak products are available
such as Intratex™ N, available from Crompton and Knowles Corp., and Erional™ PA, available
from Ciba-Geigy Corp., Nylofixan™P available from Sandoz Ltd. Mesitol™ NBS, available
from Mobay Chemical Corp., Resist #4, available from Lyndal Chemical Co., Ameriolate™,
available from American Emulsions Co. Inc. and Synthabond™ 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).
[0029] 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.
[0030] The fluorochemical compositions useful in the present invention for providing oil
and water repellency 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.) 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.).
[0031] 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 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 conditions, e.g., in an autoclave,
generally requires larger amounts of the resin than with yarn heat-set under substantially
dry conditions.
[0032] The divalent metal salts are preferably used in an amount of at least 1% owf, more
preferably at least 1.5% 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.
[0033] The fluorochemical composition, when included in the treating solution, is preferably
present in an amount of 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 material is nylon fiber, smaller denier
fiber requires larger amounts of the fluorochemical composition than larger denier
fiber.
[0034] 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 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 resin.
Surprisingly, the dye bath can be maintained in the normal pH rang 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.
[0035] Alternatively, the sulfonated novolak resin and 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
maintained at a temperature at or near boiling for a period of time sufficient to
exhaust the resin, usually 10 to 90 minutes.
[0036] The sulfonated novolak resin and divalent metal salt can be applied during continuous
dyeing, such as with Kuster™ or Otting™ 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 resin 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.
[0037] The sulfonated novolak resin and divalent salt can also be applied to polyamide material
by a padding operation. 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 agents. After application of the resin/salt solution, the polyamide material
is conventionally dried.
[0038] Fluorochemical compositions for providing oil and water repellency can also be applied
in conjunction with 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.
[0039] 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 scoured, greige, unbacked, level-loop carpet.
Preparation of a sulfonated phenol-formaldehyde resin (hereinafter SPFR):
[0040] To a three-neck flask, fitted with a mechanical stirrer, thermometer, and condenser,
was added 473 g of acetic anhydride and 945 g of 4,4ʹ-dihydroxydiphenylsulfone (DDS).
Then 473 g of conc. sulfuric acid was added via a dropping funnel over a period of
one hour with stirring. 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 for 6 hours. The resulting sulfonated 4,4ʹ-dihydroxydiphenylsulfone-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 concentrate (SPFR).
[0041] In the following examples, fibrous polyamide materials were evaluated using the following
test methods:
Stain Resistance (SR)
[0042] 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 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 satisfactory.
Water Repellency (WR)
[0043] The water repellency of treated polyamide samples is measured using a water/isopropyl
alcohol test, and is 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 of 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 amounts
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.
Oil Repellency (OR)
[0044] 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 penetration
by oils of varying surface tensions. Treated fabrics resistant only to Nujol™, 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 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 of the Standard Test. Higher numbers indicate
better oil repellency. Additionally, a value of 0 indicates no resistance to Nujol™.
In general, an oil repellency of at least 1 or greater is desirable for carpet.
Examples 1-3 and Comparative Example C1-C4
[0045] 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 Table 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 carpet 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.
![](https://data.epo.org/publication-server/image?imagePath=1993/10/DOC/EPNWB1/EP87308464NWB1/imgb0002)
[0046] 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
[0047] 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-364, 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.
![](https://data.epo.org/publication-server/image?imagePath=1993/10/DOC/EPNWB1/EP87308464NWB1/imgb0003)
[0048] 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
[0049] 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 Tectilon™
Blue 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. on 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. 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.
![](https://data.epo.org/publication-server/image?imagePath=1993/10/DOC/EPNWB1/EP87308464NWB1/imgb0004)
[0050] 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
[0051] 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.
![](https://data.epo.org/publication-server/image?imagePath=1993/10/DOC/EPNWB1/EP87308464NWB1/imgb0005)
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
[0052] Samples of chamois (natural leather) and upholstery-weight, nylon Ultrasuede™ (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.
![](https://data.epo.org/publication-server/image?imagePath=1993/10/DOC/EPNWB1/EP87308464NWB1/imgb0006)
[0053] 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
[0054] 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 pH
of about 6 and a treatment time of 90 minutes in a Launderometer. 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.
![](https://data.epo.org/publication-server/image?imagePath=1993/10/DOC/EPNWB1/EP87308464NWB1/imgb0007)
[0055] The data in Table 6 show that the good stain resistance obtained with SPFR at pH
values of 3-6 is 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
[0056] 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-214, 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.
![](https://data.epo.org/publication-server/image?imagePath=1993/10/DOC/EPNWB1/EP87308464NWB1/imgb0008)
[0057] 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.
Examples 28-42 and Comparative Examples C33-C48
[0058] 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.
![](https://data.epo.org/publication-server/image?imagePath=1993/10/DOC/EPNWB1/EP87308464NWB1/imgb0010)
Examples 43-48 and Comparative Examples C49-C51
[0059] 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 20% owf magnesium sulfate salt,
with and without 0.5% solids owf fluorochemical oil and water repellent (FC), and
with and without Tectilon™ Blue 5GS dye, available from 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.
![](https://data.epo.org/publication-server/image?imagePath=1993/10/DOC/EPNWB1/EP87308464NWB1/imgb0011)
[0060] 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.
Example 49 and Comparative Examples C52-C53
[0061] 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™ DOSS,
available from Lyndal Chemical Co., 0.25 g/l Sequesterent™ 220, available from Ciba-Geigy
Corp., 0.1 g/l sodium thiosulfate, 0.026 g/l Tectilon™ Blue 4R200, 0.032 g/l Tectilon™
Red 2B200, and 0.050 g/l Tectilon™ 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 Karawet™
DOSS. The dye bath pH was 6.0. 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.
![](https://data.epo.org/publication-server/image?imagePath=1993/10/DOC/EPNWB1/EP87308464NWB1/imgb0012)
[0062] The results in Table 10 show that only when the salt is present, is excellent stain
resistance achieved.
[0063] Various modifications and alterations of this invention will be apparent to those
skilled in the art without departing from the scope of this invention and this invention
should not be restricted to that set forth herein for illustrative purposes.
1. Verfahren zum Herstellen von verfärbungsbeständigen Polyamid-Fasermaterialien, in
dem die Polyamid Fasermaterialien mit einer wäßrigen Lösung kontaktiert werden, die
ein normalerweise festes, wasserlösliches, teilsulfoniertes Novolakharz enthält, das
wenigstens teilweise aus dem Kondensationsprodukt mindestens einer Phanolverbindung
und eines Aldehyds besteht, dadurch gekennzeichnet, daß die Lösung ferner ein wasserlösliches
Salz eines zweiwertigen Metallsalzes enthalt, das kein Salz eines Phenol-Aldehyd-Kondensationsprodukts
ist.
2. Verfahren nach Anspruch 1, in dem zu einem Färbebad vor oder nach dem Färben des Polyamidmaterials
oder während dieses Färbens eststoff des sulfonierten Novolakharzes in einer Menge
von mindestens 0,1 Gew.-%, des Polyamidmaterials und das wasserlösliche Salz eines
zweiwertigen Metalls in einer Menge von mindestens 1 Gew.-% des Polyamidmatarials
zugesetzt werden, das Polyamidmaterial in das Färbebad solange und bei einer solchen
Temperatur getaucht wird, daß das sulfonierte Novolakharz auf dem Polyamidmatarial
abgeschieden wird, das Polyamidmaterial dem Färbebad entnommen und das Polyamidmaterial
getrocknet wird.
3. Verfahren nach Anspruch 1, in dem auf das Polyamidmaterial eine Lösung aufgetragen
wird, die Festatoff des sulfonierten Novolakharzes in einer Menge von mindestens 0,1
Gew.-% das Polyamidmaterials und das wasserlösliche Salz eines zweiwertigen Metalls
in einer Menge von mindestens 1 Gew.-% des Polyamidmaterials enthält, das Polyamidmaterial
solange gedämoft wird, daß das sulfonierte Novolakharz an dem Polyamidmaterial haftet,
und das Polyamidmaterial getrocknet wird.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß auf das Polyamidmaterial eine
Lösung aufgeklotzt wird, die Feststoff des sulfonierten Novolakharzes in einer Menge
von mindestens 0,1 Gew.-% des Polyamidmaterials und das wasserlösliche Salz eines
zweiwertigen Metalls in einer Menge von mindestens 1 Gew.-% des Polyamidmaterials
enthält.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das wasserlösliche Salz eines
zweiwertigen Metalls aus den anorganischen und organischen Salzen des Magnesiums,
Bariums, Calciums und Zinks ausgewählt wird.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das sulfonierte Novolakharz
wenigstens teilweise aus einem sulfonierten Kondensationsprodukt mindestens einer
Phenolverbindung und eines Aldehyds besteht.
7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, den die wäßrige Lösung ferner eine
öl- und wasserabweisende fluorchemische Zusammensetzung enthält und daß das wasserlösliche
Metallsalz ein Magnesiumsalz ist.
8. Polyamidfasermaterial, das nach dem Verfahren nach Anspruch 1 behandelt worden ist.
9. Wäßrige Lösung vom Verfärbungsbeständigmachen von Polyamidfasermaterialien, die ein
normalerweise festes, wasserlösliches, teilsulfoniertes Novolakharz enthält, dadurch
gekennzeichnet, daß die Lösung ferner ein wasserlösliches Salz eines zweiwertigen
Metalls enthält, das kein Salz eines Phenol-Aldehyd-Kondensationsprodukts ist.
10. Lösung anch Anspruch 9, dadurch gekennzeichnet, daß die Lösung Feststoff des sulfonierten
Novolakharzes in einer Menge von mindestens 0,1 Gew.-% des Polyamid-materials und
das wasserlösliche Salz eines zweiwertigen Metalls in einer Menge von mindestens 1
Gew.-% des Polyamidmaterials enthält.
11. Lösung anch Anspruch 9, dadurch gekennzeichnet, daß die Lösung ferner eine öl- und
wasserabweisende fluorchemische Zusammensetzung enthält.
1. Procédé pour donner à des matières en polyamides fibreux une résistance aux saletés,
comprenant la mise en contact des matières en polyamides fibreux avec une solution
aqueuse comprenant une résine novolaque partiellement sulfonée, soluble dans l'eau,
normalement solide, qui comprend le produit de condensation d'au moins un composé
phénolique et d'un aldéhyde, caractérisé en ce que cette solution contient en outre
un sel soluble dans l'eau d'un métal divalent autre que celui d'un produit de condensation
de phénol/aldéhyde.
2. Procédé suivant la revendication 1, comprenant l'addition à un bain de teinture, avant,
durant ou après la teinture de la matière en polyamide, d'au moins 0,1 % de matières
solides, par rapport au poids de la matière en polyamide, de la résine novolaque sulfonée
susdite, et d'au moins 1 %, par rapport au poids de la matière en polyamide, du sel susdit, soluble dans l'eau,
d'un métal divalent, l'immersion de la matière en polyamide dans le bain de teinture
pendant une période de temps et à une température suffisantes pour épuiser la résine
novolaque sulfonée sur la matière en polyamide, l'enlèvement de la matière en polyamide
hors du bain de teinture, et le séchage de cette matière en polyamide.
3. Procédé suivant la revendication 1, comprenant l'application, à la matière en polyamide,
d'une solution comprenant au moins 0,1 % de matières solides, par rapport au poids
de la matière en polyamide, de la résine novolaque sulfonée précitée, et au moins
1 % du sel soluble dans l'eau susdit d'un métal divalent, par rapport au poids de
la matière en polyamide, le traitement à la vapeur d'eau de la matière en polyamide
susdite pendant une période de temps suffisante pour provoquer l'adhérence de cette
résine novolaque sulfonée à la matière en polyamide, et le séchage de cette dernière.
4. Procédé suivant la revendication 1, comprenant l'imprégnation d'une solution comprenant
au moins 0,1 %, par rapport au poids de la matière en polyamide, de la résine novolaque sulfonée
précitée, et au moins 1 %, par rapport au poids de la matière en polyamide, du sel soluble dans l'eau susdit
d'un métal divalent, sur la matière en polyamide, et le séchage de cette dernière.
5. Procédé suivant la revendication 1, dans lequel le sel soluble dans l'eau précité
d'un métal divalent est choisi parmi les sels inorganiques et organiques de magnésium,
de baryum, de calcium et de zinc.
6. Procédé suivant la revendication 1, dans lequel la résine de novolaque sulfonée consiste
en un produit de condensation sulfoné d'au moins un composé phénolique et d'un aldéhyde.
7. Procédé suivant la revendication 1, dans lequel la solution aqueuse précitée contient
en outre une composition fluorochimique repoussant l'huile et l'eau, et le sel de
métal soluble dans l'eau susdit est un sel de magnésium.
8. Matière en polyamide fibreux, traitée suivant le procédé de la revendication 1.
9. Solution aqueuse pour donner une résistance aux taches à des matières en polyamides
fibreux, cette solution comprenant une résine novolaque, partiellement sulfonée, soluble
dans l'eau, normalement solide, cette solution étant caractérisée en ce qu'elle contient
en outre un sel soluble dans l'eau d'un métal divalent, autre que celui d'un produit
de condensation de phénol/ aldéhyde.
10. Solution suivant la revendication 9, qui comprend au moins 0,1 % de matières solides,
par rapport au poids de la matière en polyamide, de la résine novolaque sulfonée précitée
et au moins 1 % du sel soluble susdit d'un métal divalent, par rapport au poids de
la matière en polyamide.
11. Solution suivant la revendication 9, qui comprend en outre une composition fluorochimique
repoussant l'huile et l'eau.