EP0760026B1 - Dye-retarded nylon 6/6,6 block copolymer fibers - Google Patents
Dye-retarded nylon 6/6,6 block copolymer fibers Download PDFInfo
- Publication number
- EP0760026B1 EP0760026B1 EP94916660A EP94916660A EP0760026B1 EP 0760026 B1 EP0760026 B1 EP 0760026B1 EP 94916660 A EP94916660 A EP 94916660A EP 94916660 A EP94916660 A EP 94916660A EP 0760026 B1 EP0760026 B1 EP 0760026B1
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- EP
- European Patent Office
- Prior art keywords
- nylon
- dye
- yarns
- stainblocker
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
- D06M15/412—Phenol-aldehyde or phenol-ketone resins sulfonated
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/56—Condensation products or precondensation products prepared with aldehydes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/241—Polyamides; Polyurethanes using acid dyes
Definitions
- This invention pertains to fibers comprised of nylon 6/6,6 melt-blended copolymers which have reduced acid dye rates relative to nylon 6 homopolymer fibers. More specifically, it pertains to fibers spun from block copolymers prepared by melt-blending about 2-30 wt% nylon 6,6 and about 70-98% nylon 6 polymers to yield products which exhibit a reduced dye rate relative to nylon 6 homopolymer. The reduction in dye rate is enhanced synergistically by the use of a stain-blocker.
- nylon 6 (poly( ⁇ -caprolactam)) yarns have a high acid dye rate that is further increased when the yarns are dyed in hot dyeing processes. This high dye strike rate makes it difficult to achieve uniform dyeing of substrates comprised of nylon 6 yarns.
- the dye is applied directly to the fabric at high concentration and is rapidly fixed. There is little opportunity for dye leveling to occur as it would in a beck process.
- nylon 6 yarns that results from their high dye strike rate are more readily stained by various foodstuffs containing acid dyes than similar yarns made of nylon 6,6 (poly(hexamethylene adipamide)). This is true whether the yarn has been dyed by conventional dyeing processes or is undyed, e.g., either a "white” yarn or a "producer-colored” yarn which is not dyed, but colored by the addition of colored pigments to the polymer prior to spinning. For this reason, it is more difficult to eliminate staining of both dyed and undyed nylon 6 substrates, such as carpets or other textiles, by the application of stain-resist agents.
- the present invention overcomes the above disadvantages by providing a means for producing nylon 6/6,6 melt-blended yarns having reduced acid dye rates, both when the yarn is undyed, but especially after dyeing.
- a greater than expected reduction in acid dye rate is achieved upon application of a stainblocker to the yarns.
- nylon 6 may be significantly reduced by melt-blending nylon 6 with 2-30 wt% of nylon 6,6 to form a block copolymer having two distinct melting points, one near that of nylon 6,6 and a second one near that of nylon 6.
- block copolymers are more resistant to staining by acid dyes than the corresponding nylon 6 homopolymer.
- Aftertreatment of substrates comprised of either undyed or dyed fibers of such nylon 6/6,6 block copolymers with a stain-resist agent results in a greater than expected reduction in the rate of staining by acid dyes.
- this invention relates to a fiber formed of a block copolymer of 2 to 30 weight percent poly(hexamethylene adipamide) and 70 to 98 weight percent poly( ⁇ -caprolactam) having both a first melting point near that of poly(hexamethylene adipamide) and a second melting point near that of poly( ⁇ -caprolactam) and having a stainblocker applied to the surface thereof.
- melt-blending of 70-98 wt% nylon 6 and 2-30 wt% nylon 6,6 is accomplished using methods well known in the art.
- the melt-blending is done by blending the nylon 6 and nylon 6,6 homopolymer flake in the extruder used to extrude the fibers.
- control of the moisture content of the polymer melt and the temperature thereof can be used to obtain the desired molecular weight of the product polyamide.
- molecular weights of from about 12,000 to 22,000, or having a relative viscosity (RV) of 30 to about 100, are used for spinning of nylon fibers.
- melt hold up time in the extruder, transfer line, and spin block should be from 4 to 12 minutes using a melt temperature of 270°-300°C. Using shortened holdup times or lower temperatures results in the product being a blend rather than a block copolymer, whereas the use of longer hold up times or higher temperatures can result in the product being an essentially random copolymer.
- nylon 6,6 may be supplied to the melt-zone of the extruder from a close coupled second extruder or the nylon 6,6 can be combined with the nylon 6 via transferline injection so long as the residence time is short enough to prevent random copolymerization of the two nylon components.
- the copolymers produced by this process have been characterized as having, in general, two melting peaks which are near, but somewhat below, the melt points of the individual polymers. Typically, the lower melting point will be within 10°C of the melting point of the nylon 6 polymer, while the higher melting point will be within 15°C of the melting point of the nylon 6,6 polymer.
- the melting points can readily be determined by the use of a differential scanning calorimeter measuring the melting points of the copolymer in air. They also exhibit a trace of alpha crystal form in a predominantly gamma crystal structure, indicating that the nylon 6 and nylon 6,6 are not completely copolymerized or randomized in the melt-blending process.
- the melt-blended polyamides also exhibit heats of fusion of less than about 66 cal/g.
- the copolymer fibers exhibit an acid dye rate that is lower than that of nylon 6 homopolymer fibers over the full range of compositions.
- a further, and greater than expected, decrease in this dye rate is achieved by application of a stainblocker, such as a sulphonated phenol-formaldehyde condensation product, to the fibers.
- Stainblockers are products which impart to the yarns or carpets to which they are applied resistance to staining by acid dyes of the type commonly found in various foods and beverages.
- Stainblocker compositions comprising sulfonated napthol- or sulfonated phenol-formaldehyde condensation products and methods for treating polyamide carpets or carpet yarn with these compositions to render the carpets resistant to staining by acid dyes are disclosed in Ucci and Blyth U.S. Patent No. 4,501,591, Blyth and Ucci U.S. Patent No. 4,592,940, Blyth and Ucci, U.S. Patent No. 4,680,212, and Greschler, Malone, and Zinnato U.S. Patent No. 4,780,099.
- Stain-resist agents comprised of mixtures of sulfonated phenol-formaldehyde condensation products with a hydrolyzed polymer of maleic anhydride and one or more ethylenically unsaturated aromatic monomers are described in Fitzgerald, Rao, Vinod, and Alender, U.S. Patent No. 4,883,839.
- U.S. Patent No. 4,822,373 discloses treatment of fibrous polyamide substrates to render them resistant to staining by acid dyestuffs by applying thereto a stainblocker composition
- a stainblocker composition comprising (a) a partially sulfonated novolak resin and (b) polymethacrylic acid, copolymers of methacrylic acid, or combinations of polymethacrylic acid and copolymers of methacrylic acid.
- stainblockers and methods for applying them described in the foregoing disclosures may be used in treating the fibers of this invention.
- the stainblocker can be applied before or after dyeing, but it is most commonly applied after the dyeing process.
- the stainblocker may also be applied to "producer-colored" yarns, i.e. those which are not dyed but are colored by the addition of colored pigments to the polymer prior to spinning.
- the effect of the stainblocker on these block copolymer fibers can be measured by a dye retardation factor, which is herein defined as the acid dye rate of the fiber before application of the stainblocker divided by the acid dye rate of the fiber after application of the stainblocker.
- the copolymer fibers of this invention exhibit dye retardation factors greater than 35 for unbulked fibers which have been twist-set in steam. It has been found that application of a sulphonated phenol-formaldehyde stain-resist agent to "as processed" (unheatset) yarns spun from 2% nylon 6,6 copolymer results in a decrease in acid dye rate that is three times greater than the decrease in acid dye rate achieved by application of the same stainblocker to nylon 6 homopolymer fibers. For 6% nylon 6,6 copolymer yarns, the decrease is four times greater than that achieved for nylon 6 homopolymer yarns. The effect is not as great for steam heatset yarns where for 2% nylon 6,6 copolymer, the acid dye rate decrease is two times that achieved for nylon 6 homopolymer yarns.
- Relative Viscosity is the formic acid relative viscosity as described at col. 2, lines 42-51, in Jennings, U.S. Patent No. 4,702,875.
- Amine end levels were determined by the method described beginning on page 293 in Volume 17 of the "Encyclopedia of Industrial Chemical Analysis” published by John Wiley & Sons (1973).
- Melting Points were measured using a Du Pont differential scanning calorimeter in air, the temperature being raised at a rate of 2°C per minute.
- Acid dye rates were measured using the method for determining the Cold Dye Rate of scoured yarns which is described in Windley, U.S. Patent No. 4,919,874.
- Copolymer fibers and controls were prepared by flake blending approximately 2-15 wt% nylon 6,6 having a RV of 46 and amine ends of 40.5 with 85-98 wt% nylon 6 having a RV of 43.6 and amine ends of 51.8.
- approximately 98 wt% nylon 6 was blended with 2 wt% nylon 6,6;
- approximately 94 wt% of nylon 6 was blended with 4 wt% of nylon 6,6;
- EXAMPLE 3 approximately 90 wt% of nylon 6 was blended with 10 wt% nylon 6,6; and for EXAMPLE 4, approximately 85 wt% of nylon 6 was blended with 15 wt% of nylon 6,6.
- the flake was blended at the entrance of a twin screw extruder Model 402, manufactured by Werner-Pfleiderer Corp., 663 East Crescent Avenue, Ramsey, New Jersey 07446.
- the blended flake was extruder-melted with the temperature increasing from 235° to 277°C as the polymer progressed through the screw-melter.
- the temperature was then held constant at about 279°C as the polymer passed through the transfer line, spin pump and spin pack.
- the residence time from the point of flake addition to the spinneret was approximately 10.5 minutes.
- the polymer was spun at 1.9 grams/minute/capillary into 17 filaments having a round cross-section.
- the filaments were air quenched and passed over a primary finish roll to a feed roll operating at a surface speed of 300 m/minute.
- the spun filaments were drawn at ambient temperature to 19 denier/filament (21 dtex) by rolls operating at a surface speed of 900 m/minute and then wound onto a tube at a speed of 860 m/minute.
- a nylon 6 homopolymer control sample was spun from nylon 6 containing no nylon 6,6 (Control A).
- a second homopolymer control sample of nylon 6,6 was also produced (Control B). TABLE I gives physical properties of the as-produced homopolymer and block copolymer yarns. A portion of the yarn samples were then heatset in steam in an autoclave at 132°C using a standard carpet heatset cycle excluding oxygen.
- Undyed yarns (heatset and unheatset) to be tested for acid dye rate were scoured and then dried to obtain accurate sample weights. Yarn samples of 28-30 g were scoured using the following procedure.
- the 28-30 g yarn sample was then added with occasional stirring for 20 minutes.
- the sample was then removed, washed at least 3 times in tap water, then at least 3 times in distilled water or until no evidence of soap remained, squeezed as dry as possible and put into an aluminum pan.
- pans containing yarn were placed into a forced draft oven at 40°C overnight. They were then removed to a vacuum oven at 40°C and dried under vacuum for 2 hours.
- the dried scoured (and optionally heatset) yarns were placed in a beaker in a mock dye bath at pH 4 consisting of 5 grams monobasic sodium phosphate in 1000 ml water. The yarn was removed after sitting for 15 to 20 minutes at room temperature, the water pressed out, and the yarns spun and blotted to remove excess water.
- the stain-resist bath was prepared by adding 1 g of a 30 wt% solution of a sulfonated phenol-formaldehyde condensation product (Mesitol NBS produced by Mobay Chemical Company, Penn Lincoln Parkway West, Pittsburgh, PA. 15205) in ethylene glycol in 1200 ml water in an enamel bucket. The pH was adjusted to 2.0 using sulfamic acid. Forty (40) grams of fiber were added to the bath which was then heated to 80°C. The bath was maintained at 80°C and stirred gently for 25 minutes. The yarn was then removed, rinsed, and dried overnight in an oven at 40°C and used in acid dye rate analysis testing.
- a sulfonated phenol-formaldehyde condensation product (Mesitol NBS produced by Mobay Chemical Company, Penn Lincoln Parkway West, Pittsburgh, PA. 15205)
- ethylene glycol in 1200 ml water in an enamel bucket.
- the pH was adjusted to 2.0 using sulfamic
- a dye stock solution was prepared by addition of 1 gram of Tectilon Blue 2GL (200%) (Acid Blue C.I. 40) to 1000 ml. of water.
- a mock bath (pH 7) was prepared using 5 g of monobasic sodium phosphate to 1000 ml of water. Yarn samples weighing approximately 40 grams were placed in the mock bath at 21°C for 15 minutes.
- a dye bath was prepared using 40 ml of the dye stock solution described above in a 40:1 liquor ratio. The dye bath was adjusted to pH 7 and placed on a hot plate. The yarn was added and the dye bath brought to a boil over a period of one hour. The bath was then boiled for one hour with stirring. The dye was then completely exhausted onto the fibers by lowering the pH to 2.
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Description
This invention pertains to fibers comprised of
nylon 6/6,6 melt-blended copolymers which have reduced
acid dye rates relative to nylon 6 homopolymer fibers.
More specifically, it pertains to fibers spun from block
copolymers prepared by melt-blending about 2-30 wt% nylon
6,6 and about 70-98% nylon 6 polymers to yield products
which exhibit a reduced dye rate relative to nylon 6
homopolymer. The reduction in dye rate is enhanced
synergistically by the use of a stain-blocker.
A disadvantage of nylon 6 (poly(ε-caprolactam))
yarns is that they have a high acid dye rate that is
further increased when the yarns are dyed in hot dyeing
processes. This high dye strike rate makes it difficult
to achieve uniform dyeing of substrates comprised of nylon
6 yarns. In many of the continuous dyeing processes used
today, such as Kusters, print, spray, and fluid dyeing,
the dye is applied directly to the fabric at high
concentration and is rapidly fixed. There is little
opportunity for dye leveling to occur as it would in a
beck process.
A further disadvantage of nylon 6 yarns that
results from their high dye strike rate is that they are
more readily stained by various foodstuffs containing acid
dyes than similar yarns made of nylon 6,6 (poly(hexamethylene
adipamide)). This is true whether the yarn has
been dyed by conventional dyeing processes or is undyed,
e.g., either a "white" yarn or a "producer-colored" yarn
which is not dyed, but colored by the addition of colored
pigments to the polymer prior to spinning. For this
reason, it is more difficult to eliminate staining of both
dyed and undyed nylon 6 substrates, such as carpets or
other textiles, by the application of stain-resist agents.
The present invention overcomes the above
disadvantages by providing a means for producing nylon
6/6,6 melt-blended yarns having reduced acid dye rates,
both when the yarn is undyed, but especially after dyeing.
In particular a greater than expected reduction in acid
dye rate is achieved upon application of a stainblocker to
the yarns. This results in both dyed and undyed products
comprised of these yarns which have superior stain-resistance
as compared to that of products comprised of
comparable nylon 6 homopolymer yarns and equivalent at
some compositions to nylon 6,6 yarns which have been
treated with a stain-resist agent.
It has now been found that the acid dye rate of
nylon 6 may be significantly reduced by melt-blending
nylon 6 with 2-30 wt% of nylon 6,6 to form a block
copolymer having two distinct melting points, one near
that of nylon 6,6 and a second one near that of nylon 6.
These block copolymers are more resistant to staining by
acid dyes than the corresponding nylon 6 homopolymer.
Aftertreatment of substrates comprised of either undyed or
dyed fibers of such nylon 6/6,6 block copolymers with a
stain-resist agent results in a greater than expected
reduction in the rate of staining by acid dyes.
Accordingly, this invention relates to a fiber
formed of a block copolymer of 2 to 30 weight percent
poly(hexamethylene adipamide) and 70 to 98 weight percent
poly(ε-caprolactam) having both a first melting point near
that of poly(hexamethylene adipamide) and a second melting
point near that of poly(ε-caprolactam) and having a
stainblocker applied to the surface thereof.
Melt-blending of 70-98 wt% nylon 6 and 2-30 wt%
nylon 6,6 is accomplished using methods well known in the
art. In a preferred process, the melt-blending is done by
blending the nylon 6 and nylon 6,6 homopolymer flake in
the extruder used to extrude the fibers. As is known in
the art, control of the moisture content of the polymer
melt and the temperature thereof can be used to obtain the
desired molecular weight of the product polyamide.
Typically, molecular weights of from about 12,000 to
22,000, or having a relative viscosity (RV) of 30 to about
100, are used for spinning of nylon fibers. Generally,
the melt hold up time in the extruder, transfer line, and
spin block should be from 4 to 12 minutes using a melt
temperature of 270°-300°C. Using shortened holdup times
or lower temperatures results in the product being a blend
rather than a block copolymer, whereas the use of longer
hold up times or higher temperatures can result in the
product being an essentially random copolymer.
This invention is not limited to flake-blended
nylon 6 and nylon 6,6. Other means of melt-blending known
in the art may also be used. For example, nylon 6,6 may
be supplied to the melt-zone of the extruder from a close
coupled second extruder or the nylon 6,6 can be combined
with the nylon 6 via transferline injection so long as the
residence time is short enough to prevent random
copolymerization of the two nylon components.
The copolymers produced by this process have been
characterized as having, in general, two melting peaks
which are near, but somewhat below, the melt points of the
individual polymers. Typically, the lower melting point
will be within 10°C of the melting point of the nylon 6
polymer, while the higher melting point will be within
15°C of the melting point of the nylon 6,6 polymer. The
melting points can readily be determined by the use of a
differential scanning calorimeter measuring the melting
points of the copolymer in air. They also exhibit a trace
of alpha crystal form in a predominantly gamma crystal
structure, indicating that the nylon 6 and nylon 6,6 are
not completely copolymerized or randomized in the melt-blending
process. The melt-blended polyamides also
exhibit heats of fusion of less than about 66 cal/g.
The copolymer fibers exhibit an acid dye rate that
is lower than that of nylon 6 homopolymer fibers over the
full range of compositions. A further, and greater than
expected, decrease in this dye rate is achieved by
application of a stainblocker, such as a sulphonated
phenol-formaldehyde condensation product, to the fibers.
Stainblockers (also referred to herein as stain-resists
or stain-resist agents) are products which impart
to the yarns or carpets to which they are applied
resistance to staining by acid dyes of the type commonly
found in various foods and beverages. Stainblocker
compositions comprising sulfonated napthol- or sulfonated
phenol-formaldehyde condensation products and methods for
treating polyamide carpets or carpet yarn with these
compositions to render the carpets resistant to staining
by acid dyes are disclosed in Ucci and Blyth U.S. Patent
No. 4,501,591, Blyth and Ucci U.S. Patent No. 4,592,940,
Blyth and Ucci, U.S. Patent No. 4,680,212, and Greschler,
Malone, and Zinnato U.S. Patent No. 4,780,099.
Stain-resist agents comprised of mixtures of
sulfonated phenol-formaldehyde condensation products with
a hydrolyzed polymer of maleic anhydride and one or more
ethylenically unsaturated aromatic monomers are described
in Fitzgerald, Rao, Vinod, and Alender, U.S. Patent No.
4,883,839.
Olson, Chang, and Muggli, U.S. Patent No.
4,822,373 discloses treatment of fibrous polyamide
substrates to render them resistant to staining by acid
dyestuffs by applying thereto a stainblocker composition
comprising (a) a partially sulfonated novolak resin and
(b) polymethacrylic acid, copolymers of methacrylic acid,
or combinations of polymethacrylic acid and copolymers of
methacrylic acid.
Chang, Olson, and Muggli, EPO Published
Application 332,342 discloses a method for imparting stain
resistance to fibrous polyamide materials that involves
contacting the materials with an aqueous solution
comprising polymethacrylic acid, copolymers of methacrylic
acid, or combinations thereof.
U.S. Patent 4,940,757 to Moss et al. describes
stain-resist compositions comprising the product prepared
by polymerizing any of various alpha-substituted acrylic
acids in the presence of a sulfonated aromatic
formaldehyde condensation product.
Any of the stainblockers and methods for applying
them described in the foregoing disclosures may be used in
treating the fibers of this invention. The stainblocker
can be applied before or after dyeing, but it is most
commonly applied after the dyeing process. The
stainblocker may also be applied to "producer-colored"
yarns, i.e. those which are not dyed but are colored by
the addition of colored pigments to the polymer prior to
spinning. The effect of the stainblocker on these block
copolymer fibers can be measured by a dye retardation
factor, which is herein defined as the acid dye rate of
the fiber before application of the stainblocker divided
by the acid dye rate of the fiber after application of the
stainblocker. This factor is a measure of the magnitude
of the effect of the stainblocker on the acid dye rate of
a fiber. The copolymer fibers of this invention exhibit
dye retardation factors greater than 35 for unbulked
fibers which have been twist-set in steam. It has been
found that application of a sulphonated phenol-formaldehyde
stain-resist agent to "as processed"
(unheatset) yarns spun from 2% nylon 6,6 copolymer results
in a decrease in acid dye rate that is three times greater
than the decrease in acid dye rate achieved by application
of the same stainblocker to nylon 6 homopolymer fibers.
For 6% nylon 6,6 copolymer yarns, the decrease is four
times greater than that achieved for nylon 6 homopolymer
yarns. The effect is not as great for steam heatset yarns
where for 2% nylon 6,6 copolymer, the acid dye rate
decrease is two times that achieved for nylon 6
homopolymer yarns.
Relative Viscosity (RV) is the formic acid
relative viscosity as described at col. 2, lines 42-51, in
Jennings, U.S. Patent No. 4,702,875.
Amine end levels were determined by the method
described beginning on page 293 in Volume 17 of the
"Encyclopedia of Industrial Chemical Analysis" published
by John Wiley & Sons (1973).
Melting Points were measured using a Du Pont
differential scanning calorimeter in air, the temperature
being raised at a rate of 2°C per minute.
Acid dye rates were measured using the method for
determining the Cold Dye Rate of scoured yarns which is
described in Windley, U.S. Patent No. 4,919,874.
The following examples are offered for the purpose
of illustrating the invention and are not intended to be
limiting. Percentages are by weight except where
otherwise indicated.
Copolymer fibers and controls were prepared by
flake blending approximately 2-15 wt% nylon 6,6 having a
RV of 46 and amine ends of 40.5 with 85-98 wt% nylon 6
having a RV of 43.6 and amine ends of 51.8. For EXAMPLE
1, approximately 98 wt% nylon 6 was blended with 2 wt%
nylon 6,6; for EXAMPLE 2, approximately 94 wt% of nylon 6
was blended with 4 wt% of nylon 6,6; for EXAMPLE 3,
approximately 90 wt% of nylon 6 was blended with 10 wt%
nylon 6,6; and for EXAMPLE 4, approximately 85 wt% of
nylon 6 was blended with 15 wt% of nylon 6,6. The flake
was blended at the entrance of a twin screw extruder Model
402, manufactured by Werner-Pfleiderer Corp., 663 East
Crescent Avenue, Ramsey, New Jersey 07446. The blended
flake was extruder-melted with the temperature increasing
from 235° to 277°C as the polymer progressed through the
screw-melter. The temperature was then held constant at
about 279°C as the polymer passed through the transfer
line, spin pump and spin pack. The residence time from
the point of flake addition to the spinneret was
approximately 10.5 minutes. The polymer was spun at 1.9
grams/minute/capillary into 17 filaments having a round
cross-section. The filaments were air quenched and passed
over a primary finish roll to a feed roll operating at a
surface speed of 300 m/minute. The spun filaments were
drawn at ambient temperature to 19 denier/filament (21
dtex) by rolls operating at a surface speed of 900
m/minute and then wound onto a tube at a speed of 860
m/minute. A nylon 6 homopolymer control sample was spun
from nylon 6 containing no nylon 6,6 (Control A). A
second homopolymer control sample of nylon 6,6 was also
produced (Control B). TABLE I gives physical properties
of the as-produced homopolymer and block copolymer yarns.
A portion of the yarn samples were then heatset in steam
in an autoclave at 132°C using a standard carpet heatset
cycle excluding oxygen.
| 6/6,6 WT% RATIO | HEAT OF FUSION IN J/G (CAL/G) | MELTING POINT (°C) | |||
| 6 | 6,6 | RV | |||
| Control A | 100/0 | 275 (65.7) | 220.2 | --- | 39.3 |
| EXAMPLE 1 | 98/2 | 266 (63.7) | 217.8 | 249.9 | 40.1 |
| EXAMPLE 2 | 94/6 | 225 (53.9) | 218.5 | 250.3 | 38.9 |
| EXAMPLE 3 | 90/10 | 234 (56.0) | 218.7 | 250.3 | 40.9 |
| EXAMPLE 4 | 85/15 | 239 (57.2) | 218.7 | 252.0 | 40.8 |
| Control B | 0/100 | 301 (72.1) | --- | 260.3 | 41.2 |
Undyed yarns (heatset and unheatset) to be
tested for acid dye rate were scoured and then dried to
obtain accurate sample weights. Yarn samples of 28-30 g
were scoured using the following procedure.
A one-liter bath containing in solution 1.0 g
sodium perborate and 0.25 g Igepon T-51, an anionic
surfactant used as a scouring agent for removing finish
oil produced by GAF Chemical Company, 1351 Alps Road,
Wayne, New Jersey 07470, was brought to a rolling boil.
The 28-30 g yarn sample was then added with occasional
stirring for 20 minutes. The sample was then removed,
washed at least 3 times in tap water, then at least 3
times in distilled water or until no evidence of soap
remained, squeezed as dry as possible and put into an
aluminum pan.
After scouring, the pans containing yarn were
placed into a forced draft oven at 40°C overnight. They
were then removed to a vacuum oven at 40°C and dried under
vacuum for 2 hours.
A portion of the scoured yarns were then treated
with stainblocker according to the following procedure.
The dried scoured (and optionally heatset) yarns
were placed in a beaker in a mock dye bath at pH 4
consisting of 5 grams monobasic sodium phosphate in 1000
ml water. The yarn was removed after sitting for 15 to 20
minutes at room temperature, the water pressed out, and
the yarns spun and blotted to remove excess water.
The stain-resist bath was prepared by adding 1 g
of a 30 wt% solution of a sulfonated phenol-formaldehyde
condensation product (Mesitol NBS produced by Mobay
Chemical Company, Penn Lincoln Parkway West, Pittsburgh,
PA. 15205) in ethylene glycol in 1200 ml water in an
enamel bucket. The pH was adjusted to 2.0 using sulfamic
acid. Forty (40) grams of fiber were added to the bath
which was then heated to 80°C. The bath was maintained at
80°C and stirred gently for 25 minutes. The yarn was then
removed, rinsed, and dried overnight in an oven at 40°C
and used in acid dye rate analysis testing.
TABLE II gives acid dye rates for undyed fibers
and for undyed fibers which have been treated with a
stainblocker.
| UNDYED YARN PROPERTIES WITH AND WITHOUT STAINBLOCKER AFTERTREATMENT | ||||
| DYE RATE SCOURED (X10-5 SEC-1) | DYE RATE SCOURED, W/ STAINBLOCKER (X10-5 SEC-1) | DYE RATE HEATSET (X10-5 SEC-1) | DYE RATE HEATSET, W/ STAINBLOCKER (X10-5 SEC-1) | |
| Control A | 111.0 | 2.300 | 605.5 | 16.90 |
| EXAMPLE 1 | 102.2 | 0.734 | 559.8 | 8.94 |
| EXAMPLE 2 | 98.3 | 0.480 | 428.3 | 9.94 |
| EXAMPLE 3 | 90.2 | 1.200 | 462.3 | 8.07 |
| Control B | 21.7 | 1.080 | 64.8 | 1.31 |
| DYE RETARDATION FACTOR, SCOURED | DYE RETARDATION FACTOR, HEATSET | |||
| Control A | 48.3 | 35.5 | ||
| EXAMPLE 1 | 139.8 | 62.6 | ||
| EXAMPLE 2 | 204.8 | 47.4 | ||
| EXAMPLE 3 | 75.1 | 57.2 | ||
| Control B | 20.1 | 49.4 |
A portion of the undyed, scoured, unheat-set yarns
were dyed in a simulated beck dyeing procedure described
below prior to treatment with the stainblocker.
A dye stock solution was prepared by addition of 1
gram of Tectilon Blue 2GL (200%) (Acid Blue C.I. 40) to
1000 ml. of water. A mock bath (pH 7) was prepared using
5 g of monobasic sodium phosphate to 1000 ml of water.
Yarn samples weighing approximately 40 grams were placed
in the mock bath at 21°C for 15 minutes. A dye bath was
prepared using 40 ml of the dye stock solution described
above in a 40:1 liquor ratio. The dye bath was adjusted
to pH 7 and placed on a hot plate. The yarn was added and
the dye bath brought to a boil over a period of one hour.
The bath was then boiled for one hour with stirring. The
dye was then completely exhausted onto the fibers by
lowering the pH to 2.
A portion of the dyed yarn samples were then
treated with stainblocker according to the procedure
described above. The acid dye rates of each of these dyed
yarns, including those which were stainblocker-treated,
were then measured. Results are shown in Table III.
| DYED YARN PROPERTIES WITH AND WITHOUT STAINBLOCKER AFTERTREATMENT | ||||
| 6/6,6 WT. RATIO | DYE RATE (X10-5 SEC-1) | DYE RATE W/STAINBLOCKER (X10-5 SEC-1) | DYE RETARD'N FACTOR | |
| Control A | 100/0 | 191.5 | 0.94 | 203.7 |
| EXAMPLE 2 | 94/6 | 137.4 | 0.61 | 225.2 |
| EXAMPLE 3 | 90/10 | 97.4 | 0.79 | 123.3 |
| EXAMPLE 4 | 85/15 | 91.6 | 0.23 | 398.3 |
| Control B | 0/100 | 30.4 | 0.50 | 60.8 |
Claims (5)
- A fiber formed of a block copolymer of 2 to 30 weight percent poly(hexamethylene adipamide) and 70 to 98 weight percent poly(ε-caprolactam) having both a first melting point near that of poly(hexamethylene adipamide) and a second melting point near that of poly(ε-caprolactam) and having a stainblocker applied to the surface thereof.
- A fiber of claim 1 formed of a block copolymer of 2 to 15 weight percent poly(hexamethylene adipamide) and 85 to 98 weight percent poly(ε-caprolactam).
- A fiber of claim 2 wherein the fiber is dyed.
- A fiber of claim 2 wherein the stain-blocker is a phenol-formaldehyde condensation product.
- A fiber of claim 3 wherein the stain-blocker is a phenol-formaldehyde condensation product.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1994/004966 WO1995030784A1 (en) | 1994-05-10 | 1994-05-10 | Dye-retarded nylon 6/6,6 block copolymer fibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0760026A1 EP0760026A1 (en) | 1997-03-05 |
| EP0760026B1 true EP0760026B1 (en) | 1999-09-22 |
Family
ID=22242532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94916660A Expired - Lifetime EP0760026B1 (en) | 1994-05-10 | 1994-05-10 | Dye-retarded nylon 6/6,6 block copolymer fibers |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0760026B1 (en) |
| DE (1) | DE69420866D1 (en) |
| WO (1) | WO1995030784A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9416270B2 (en) | 2011-11-14 | 2016-08-16 | Honeywell International Inc. | Polyamide composition for low temperature applications |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120094059A1 (en) * | 2009-05-11 | 2012-04-19 | Invista North America S.A R.L. | Nylon carpet fibers having bleach resistance |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4142031A (en) * | 1977-10-27 | 1979-02-27 | Toray Industries, Inc. | Polycaprolactam composition having improved melt spinnability and method for improving melt spinnability of polycaprolactam |
| DE3006500A1 (en) * | 1980-02-21 | 1981-09-03 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING POLYAMIDE FILMS |
| US4729923A (en) * | 1986-05-06 | 1988-03-08 | E. I. Du Pont De Nemours And Company | Nylon containing metal salts |
| CA2020492A1 (en) * | 1989-07-17 | 1991-01-18 | Matthew B. Hoyt | Polyamide fibers having reduced amino end groups, light-dyed and stain resistant polyamide fibers made therefrom, and method of preparation |
| US5155178A (en) * | 1990-08-08 | 1992-10-13 | E. I. Du Pont De Nemours And Company | Antistain block copolymer compositions of modified nylon copolymers and high carbon nylons |
| US5330834A (en) * | 1992-05-12 | 1994-07-19 | E. I. Du Pont De Nemours And Company | Dye-retarded nylon 6/6,6 block copolymer fibers |
-
1994
- 1994-05-10 DE DE69420866T patent/DE69420866D1/en not_active Expired - Lifetime
- 1994-05-10 WO PCT/US1994/004966 patent/WO1995030784A1/en active IP Right Grant
- 1994-05-10 EP EP94916660A patent/EP0760026B1/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9416270B2 (en) | 2011-11-14 | 2016-08-16 | Honeywell International Inc. | Polyamide composition for low temperature applications |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69420866D1 (en) | 1999-10-28 |
| JPH09512866A (en) | 1997-12-22 |
| EP0760026A1 (en) | 1997-03-05 |
| WO1995030784A1 (en) | 1995-11-16 |
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