JP3004054B2 - Dye-suppressed nylon 6 / 6,6 block copolymer fiber - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to nylon 6 / 6,6 which reduces the acid dye rate as compared to nylon 6 homopolymer fibers.
The present invention relates to a fiber containing a melt-blended copolymer. further,
In order to obtain a product exhibiting a slower dye rate compared to nylon 6 homopolymer, nylon 6,6 is used in an amount of about 2 to 30% by weight,
And a fiber spun from a block copolymer prepared by melt blending 70-98% by weight of a nylon 6 polymer. The reduction in dye speed is synergistically increased by the use of a stain-blocker.

A disadvantage of nylon 6 (poly (ε-caprolactam)) yarns is that the yarns have a further increased high acid dye rate when dyed by the thermal dyeing process. This high dye strike rate makes it difficult to achieve a uniform dyeing of the substrate containing nylon 6 yarn. In many continuous dyeing methods used today, such as Kusters, print, spray, and fluid dyeing, the dye is applied directly to the fabric at high concentrations and quickly fixed. Beck method (be
As in the case of the ck process), there is little opportunity for dye leveling to occur.

A further disadvantage of nylon 6 yarns resulting from high dye strike rates is that they are more easily made by various foodstuffs containing acidic dyes than similar yarns made from nylon 6,6 (poly (hexamethylene adipamide)). Is to be dyed. This means that, whether the yarn is dyed by conventional dyeing methods, for example, a "white dyed" yarn or a "manufacturer tinted" dyed by adding a colored pigment to the polymer which is not dyed but before spinning. (Producer-co
lored) "It is true that they are not dyed like yarn. For this reason, it is more difficult to prevent staining of both dyed and undyed nylon 6 fabrics, such as carpets or other textiles, with dye-resistant agents.

The present invention has the above disadvantages by providing a means of producing nylon 6 / 6,6 melt-blended yarn having reduced acid dye speed, both when the yarn is not dyed and especially after dyeing. Solve. In particular, greater than expected reductions in acid dye rates are achieved with the use of stain barriers on the yarn. This results in dyed and undyed products comprising these yarns having superior stain resistance compared to products comprising comparable nylon 6 homopolymer yarns, and in certain compositions, a stain resistant agent Yields an equivalent to nylon 6,6 yarn treated with

Summary of the Invention The acid dye rate of nylon 6 is 2-30 for nylon 6,6.
By melting and blending weight percent and nylon 6, the block copolymer has two different melting points, one near the melting point of nylon 6,6 and the other near the melting point of nylon 6, I do. These block copolymers are more resistant to acid dye contamination than the corresponding nylon 6 homopolymer. Post-treatment of fabrics containing undyed or dyed fibers of such nylon 6 / 6,6 block copolymers with stainproofing agents leads to a greater than expected decrease in the rate of staining with acid dyes. Bring.

Therefore, the present invention relates to a poly (hexamethylene adipamide) 2-30% by weight and poly (ε-caprolactam) 70
For fibers formed of a block copolymer containing 9898% by weight, the block copolymer having a first melting point close to the melting point of poly (hexamethylene adipamide) and a melting point of poly (ε-caprolactam) With both a second melting point close to and having a stain barrier applied to its surface.

DETAILED DESCRIPTION OF THE INVENTION 70-98% by weight nylon 6 and 2-30% by weight nylon
The 6,6 melt blending is done using methods well known in the art. In a preferred method, melt compounding is accomplished by compounding nylon 6 and nylon 6,6 homopolymer flakes in an extruder used to extrude fibers. As is known in the art, adjustment of the moisture and temperature of the polymer melt is used to obtain a product polyamide of the desired molecular weight. Typically,
Molecular weight about 12,000-22,000, or relative viscosity (RV) 30-about
Those having 100 are used for spinning nylon fibers.
Generally, the melt retention time in the extruder, transfer line, and spinning block is 4 to 4 using a melt temperature of 270 to 300 ° C.
12 minutes. The use of shorter retention times and lower temperatures results in products that are more compound than block copolymers, but products that use longer retention times or higher temperatures are essentially random copolymers Is generated.

The present invention is not limited to flaked nylon 6 and nylon 6,6. Other melt compounding means known in the art may also be used. For example, nylon 6,
6 may be fed to the melt portion of the extruder from a closely located second extruder, or the residence time is short enough to prevent random copolymerization of the two nylon components. In some cases, nylon 6,6 may be coupled to nylon 6 via transfer line injection.

Copolymers made by this method are characterized as having two dissolution peaks that are generally close to the individual polymer melting point, but somewhat lower. Typically, the lower melting point is the melting point of the nylon 6 polymer.
Within 10 ° C., the higher melting point is within 15 ° C. of the melting point of nylon 6,6 polymer. Melting points are readily determined using a differential scanning calorimeter which measures the melting point of the copolymer in air. These show traces of the alpha crystal form in the predominant gamma crystal structure, indicating that nylon 6 and nylon 6,6 are not completely copolymerized or completely randomized in the melt compounding process. Means. The melt-blended polyamide also exhibits a heat of fusion of less than about 66 cal / g.

The copolymer fibers are nylon 6 over all compositions.
The acid dye rate is lower than that of the homopolymer fibers. By using a stain barrier such as a sulfonated phenol-formaldehyde condensate on the fibers, this greater reduction in dye rate than expected is achieved.

Stain barrier agents (herein referred to as stain-resists or stain-resist agents) are used in various food and beverage applications for the yarn or carpet to which the product is applied. A product that provides resistance to contamination by acid dyes of the type commonly found in Pollution barrier compositions containing sulfonated naphthol-formaldehyde or sulfonated phenol-formaldehyde condensates and methods of processing polyamide carpets or carpet yarns with these compositions to provide carpets that resist contamination by acid dyes Is Uc
ci and Blyth in U.S. Patent No.
h and Ucci in U.S. Pat.No. 4,592,940, Blyth
And Ucci in U.S. Pat.No. 4,680,212, and G
U.S. Patent No. by reschler, Malone, and Zinnato
No. 4,780,099.

Stain-resistant agents containing a mixture of a sulfonated phenol-formaldehyde condensate and a hydrolyzed polymer of maleic anhydride and one or more ethylenically unsaturated aromatic monomers are described in Fitzgerald, Rao, Vinod, and Al.
described in U.S. Pat. No. 4,883,839 to ender.

U.S. Patent No. 4,822, by Olson, Chang, and Muggli
By applying the pollution blocking composition to No. 373,
Disclosed is the treatment of polyamide fiber fabrics to provide resistance to staining by acid dyes, the stain-blocking composition comprising (a) a partially sulfonated novolak resin and (b) polymethacrylic acid. , A copolymer of methacrylic acid, or a combination of a copolymer of polymethacrylic acid and methacrylic acid.

EP-A-332,342 by Chang, Olson and Muggli discloses a method for imparting stain resistance to polyamide fiber materials, which comprises polymethacrylic acid, copolymers of methacrylic acid, or combinations thereof. Contacting the aqueous solution with the material.

U.S. Pat.No. 4,940,757 to Moss et al. Describes a stain resistant composition, which polymerizes any of a variety of alpha-substituted acrylic acids in the presence of a sulfonated aromatic formaldehyde condensate. Product produced by the process.

Any of the soil barrier agents and methods described above for application to fibers can be used to treat the fibers of the present invention. Stain blocking agents are applied before or after dyeing, but are most commonly applied after the dyeing step. Stain blocking agents may also be applied to "manufacturer-colored" yarns, i.e., those yarns that have not been dyed but have been colored by the addition of colored pigments to the polymer prior to spinning. The effect of the stain barrier on these block copolymer fibers is measured by the dye retardation factor, where the delay factor determines the acid dye rate of the fiber prior to the application of the stain barrier, the application of the stain barrier. It is defined as divided by the acid dye rate of the subsequent fiber. This factor is a measure of the magnitude of the effect of the stain barrier on the acid dye rate of the fiber. The copolymer fibers of the present invention exhibit a dye retardation factor greater than 35 for fibers that are not twisted or bulked with steam. Sulfonated phenol to "as processed" (not heat set) yarn spun from a copolymer containing 2% nylon 6,6-
It has been found that the application of the formaldehyde stain resistant agent results in a reduction of the acid dye rate that is three times greater than the acid dye rate achieved by applying the same stain barrier to nylon 6 homopolymer fibers. For copolymer yarns containing 6% nylon 6,6, the decrease is
Four times larger than that achieved with nylon 6 homopolymer yarns. The effect on steam heat set yarns for copolymers containing 2% nylon 6,6 is not very large and the acid dye rate loss is about twice that achieved for nylon 6 homopolymer yarns.

Test Methods Relative viscosity (RV) was determined by Jennings in US Pat. No. 4,702,
Relative viscosity of formic acid as described in column 875, column 2, lines 42-51.

Amine terminal levels are described in the Encyclopedia of Industrial Chemical Analysis, published by John Wiley & Sons.
No. 29 of No. 17 of Industrial Chemical Analysis)
Determined using the method described beginning on page 3.

Melting points were measured using a Du Pont differential scanning calorimeter in air at an increasing temperature of 2 ° C. per minute.

Acid dye rates are described by Windley in U.S. Patent No. 4,919,874.
Cold Dye Speed of Washed Yarn (Cold Dye
Rate).

Examples The following examples are provided for the purpose of illustrating the invention and are not meant to be limiting. Percentages are by weight unless otherwise indicated.

The copolymer fiber and the control consist of about 2-15% by weight of RV46 and nylon 6,6 with amine ends 40.5, RV4
Nylon 6 with 3.6 and amino terminus 51.8 from 85 to 98
% By weight flakes. In Example 1, about 98% by weight of nylon 6 was added to 2% by weight.
In Example 2, about 94% by weight of nylon 6 was blended with 4% by weight of nylon 6,6, and in Example 3, about 90% by weight of nylon 6 was 10% by weight. Nylon
6,6, and in Example 4, about 85% by weight of nylon 6
Was blended with 15% by weight of nylon 6,6. The flakes were compounded at the inlet of a twin screw extruder Model 402. This extruder is manufactured by Werner-Pfleiderer Corp. (663 East Cre
scent Avenue, Ramsey, New Jersey 07446). The compounded flakes have a temperature of 235-2 as the polymer passes through the screw melter.
It was extruded and heated to 77 ° C. The temperature was then kept constant at about 279 ° C. as the polymer passed through the transfer line, spin pump and spin pack. The dwell time from the flake addition point to the spinneret was about 10.5 minutes. The polymer was spun at 1.9 grams / minute / capillary into 17 filaments with a round cross section. The filament was air quenched and passed over a first finishing roll to a feed roll operating at a surface speed of 300 m / min. The spun filament was drawn at ambient temperature by a roll operating at a surface speed of 900 m / min to 19 denier / filament (21 dtex) and wound on a tube at a speed of 860 m / min. A nylon 6 homopolymer control sample was spun from nylon 6 without nylon 6,6 (control A). A second homopolymer control sample of nylon 6,6 was also made (control B). Table I shows the physical properties of the as-produced homopolymer and block copolymer yarns. A portion of the sample yarn was heat set with steam in an autoclave at 132 ° C. using a standard carpet heat set cycle, excluding oxygen.

Undyed yarn (heat set and not heat set) tested against acid dye speed
Was washed and dried to obtain the correct sample weight.
28-30 g of sample yarn was washed using the following procedure.

A bath containing a solution of 1.0 g of sodium peroxoborate and 0.25 g of the anionic surfactant IgeponT-51 used as a detergent to remove finishing oil was transported to a rotating boiler. The surfactant here is GA
F Chemical Company (1351 Alps Road, Wayne, New
Jersey 07470). Then 28-30 g of sample yarn was added with occasional stirring for 20 minutes. The sample is then removed and washed at least three times with tap water and at least three times with distilled water or until no traces of soap remain,
It was squeezed as dry as possible and placed in an aluminum pan.

After washing, the pan containing the thread was placed in a forced air oven at 40 ° C. overnight. Then, these were transferred to a vacuum furnace at 40 ° C.
Dry under vacuum over time.

The washed thread portion was then treated with a stain barrier according to the following procedure.

The washed and dried (and optionally heat set) yarn was placed in a beaker in a mock dye bath at pH 4 consisting of 5 g of sodium monobasic phosphate in 1000 ml of water. The yarn was removed after standing at room temperature for 15-20 minutes, the water was pressed out, and the yarn was spun and blotted to remove excess water.

The stain resistant bath contains a sulfonated phenol formaldehyde condensation product in ethyl glycol (Mobay Che
mical Company (Penn Lincoln Parkway West, Pitt
Mesitol NBS manufactured by H.sburgh, PA.15205)
1g of a 30% by weight solution in water in an enamel bucket
Prepared by adding inside. The pH was adjusted to 2.0 using amidosulfuric acid. Forty grams of fiber was added to a bath heated to 80 ° C. The bath was kept at 80 ° C. and gently stirred for 25 minutes. The thread is removed and rinsed, 40
Dried in an oven at 0 ° C. overnight and used for acid dye kinetic tests.

Table II shows the acid dye rates for undyed fibers and undyed fibers treated with a stain barrier.

The dyed, washed, non-heat-set yarn sections were dyed by the similar Beck dyeing method described below before being treated with a stain barrier.

Dye preservation solution is water 1000ml, Tektilon blue 2GL
(Tectilon Blue) (200%) (Acid Blue CI4
0) Manufactured by adding 1 g. Mock bath (m
(ock bath) (pH 7) was prepared using 5 g of monobasic sodium phosphate in 1000 ml of water. A sample yarn weighing about 40 g was placed in a mock bath at 21 ° C. for 15 minutes. The dye bath was prepared using 40 ml of the dye stock solution described above at a liquor ratio of 40: 1. The dye bath was adjusted to pH 7 and placed on a hot plate. The yarn was added and the dye bath was boiled for 1 hour. The bath was boiled for one hour with stirring. The dye was then completely exhausted on the fiber by lowering the pH to 2.

A portion of the dyed sample yarn was treated with a stain barrier using the procedure described above. The acid dye rate of each of these dyed yarns, including those treated with the stain barrier, was measured. The results are shown in Table III.

Claims (5)

(57) [Claims] 1. Poly (hexamethylene adipamide)
A fiber formed from a block copolymer of 30% by weight and 70 to 98% by weight of poly (ε-caprolactam), a first melting point close to the melting point of poly (hexamethylene adipamide), and poly (ε-caprolactam) Fibers having both a second melting point close to the melting point of the fibers and having a pollution barrier applied to these surfaces. 2. Poly (hexamethylene adipamide)
The fiber of claim 1, wherein the fiber is formed from a block copolymer of 15% by weight and 85-98% by weight of poly (ε-caprolactam). 3. The fiber according to claim 2, wherein the fiber is dyed. 4. The fiber according to claim 2, wherein the pollution blocking agent is a phenol-formaldehyde condensate. 5. The fiber according to claim 3, wherein the pollution blocking agent is a phenol-formaldehyde condensate.