JPH08246352A - Stain-resistant nylon fiber - Google Patents

Abstract

(57) Abstract: To provide a nylon fiber which is not easily affected by acid dyes at ambient temperature but can be dyed at high temperature. SOLUTION: The nylon fiber is a nylon fiber having a coating containing a specific stain-blocking agent and having a "dye absorption test value" of 7% or less at 25 ° C and 30% or more at 100 ° C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to nylon fibers having exceptional and advantageous dyeing properties. In particular, the present invention is
The present invention relates to a nylon fiber which is less susceptible to stains by an acid dye at ambient temperature, but can be dyed at a high temperature without losing stain resistance by the acid dye at ambient temperature.
Normal nylon fiber is used for drinks, food, cosmetics, pharmaceuticals,
It may be permanently soiled at room temperature by acid dye colorants commonly found in household items such as. The nylon fibers of the present invention have the ability to resist the stains that normally occur with their colorants at room temperature and are therefore particularly suitable for use in carpet manufacture.

The term fiber as used herein includes very long fibers [ie filaments] and short length fibers (ie staples). The term yarn as used herein means a continuous yarn composed of a plurality of fibers.

The terms "dirt" and "dirt" as used herein with respect to nylon fibers means the discoloration of the fibers caused by the chemical reaction of compounds such as acid dyes with nylon fibers.

[0004]

Carpets made from nylon fibers are a common floor covering in both residential and commercial applications. Such carpets are relatively cheap,
It provides the desired combination of properties such as durability, aesthetics, comfort, safety, warmth and sound deadening. You can also get various attractive colors, patterns and textures. However, nylon fiber is Kool Aid
Carpets made from nylon fibers can be severely and permanently soiled by some of the artificial and natural colorants present in common household items such as and other soft drink beverages, thus spilling such items. Is easily damaged by.
Most of these colorants are acid dyes, all of which are accepted by the Food, Medicine and Cosmetics Commission for human consumption. FD & C Red Dey No. 40 is one of the most commonly used acid dye colorants that most severely stains nylon at room temperature.
(Hereinafter referred to as "Red Die No. 40"). Red Dye No. 40 (also known as CT FoodRed 17) has the following structure:

[0005]

[Chemical 17]

Nylon fibers are often coated with a fluorochemical before or after being made into a carpet for the purpose of improving the dirt resistance properties of the carpet surface. Fluorine compounds reduce the tendency of soils to adhere to the fibers, thereby making soiling stains from carpet much easier than without fluorine compounds.

[0007]

This treatment with a fluorine compound also reduces the wettability of the fiber, but for a spilled beverage containing an acid dye colorant, such a colorant is added for 5 minutes or more.
The carpet is very poorly protected unless it is removed from the carpet within 7 minutes without delay. Acid dye colorants such as Red Dye No. 40 penetrate nylon, as opposed to substances such as lipsticks, shoelaces and motor oils, which can be physically removed from nylon carpet by well known cleaning methods. , Chemically reacts with it to form a bond that renders it impossible to completely remove such colorants from nylon fibers. In fact
Within minutes, these fibers are dyed with their colorants and are therefore permanently soiled.

Looking over the carpet replacement market, it can be seen that more carpet is replaced by dirt rather than by abrasion. Therefore, there is a need in the art to provide nylon carpet fibers that can make carpets that are less susceptible to soiling.

[0009]

The present invention is less susceptible to staining with acid dye colorants at ambient temperatures, but does not lose the stain resistance to acid dye colorants at those ambient temperatures, and at high temperatures it does not. It gives a nylon fiber which can be dyed with an acid dye in a fashion. The nylon fiber of the present invention has a “dye absorption test value” defined later of 7% at 25 ° C.
It is characterized by having on its surface a coating containing one or more Stainblockers in an amount sufficient to give a fiber which is below 30% at 100 ° C.

The term "dirt blocker" as used herein means that when applied to nylon fibers as a coating in an amount of 0.35% or less based on the weight of the fiber, the dye absorption test value at 25 ° C is 7% or less. At 100 ° C, it means a compound that gives fibers that are 30% or more.

The fibers of this invention are particularly useful in providing a stain resistant nylon carpet. Such carpets can be spilled in large amounts of acid dye colorant-containing materials such as red wine and soft drinks and not soiled upon prolonged exposure.

According to a preferred embodiment of the present invention, the coating on the surface of the fibers comprises, in addition to one or more stain-blocking agents, one or more fluorine compounds, when the fibers are used in the manufacture of carpets, 30,000 cycles. Includes a sufficient amount of fiber to provide a carpet that, even after exposure to traffic, gives the carpet a greater degree of maintenance of the carpet's initial stain resistance than that of the corresponding carpet without the fluorinated compound. .
The term "traffic" as used herein means that an individual has taken a walk across a carpet. "Initial stain resistance" means the stain resistance of a new carpet before it is exposed to traffic or other abrasion of the carpet. The fluorinated compound itself does not impart sufficient stain resistance to the nylon fiber, and when used in conjunction with a stain barrier, it first provides a better stain resistance than the stain barrier itself (ie, traffic). Not before). However, it was quite unexpected that the use of one or more fluorine compounds in combination with a soil barrier would better maintain the initial soil resistance imparted to the fiber by the soil barrier.

[0013]

DETAILED DESCRIPTION OF THE INVENTION Any nylon fiber may be coated in accordance with the present invention. Commercially important nylon fibers are fibers formed from nylon 66 (polyhexamethylene adipamide) and nylon 6 (polycaprolactam). The present invention is particularly useful because it provides a nylon carpet yarn that can be made into a stain resistant carpet. The coating is preferably applied to the nylon fibers with a finish (spin finish) in the melt spinning process used to make the fibers. Appropriate amounts of soil release agents and fluorine compounds are typically incorporated into the finish, including lubricating oils for fibers and dispersants for such oils.

Soil barrier agents that are particularly useful in the practice of the present invention include, for example, condensation polymer products consisting essentially of repeating units of the formula:

[0015]

Embedded image

(Wherein R is the same or different in each unit,
Hydrogen or, -SO ₃ X,

[0017]

[Chemical 19]

And

[0019]

Embedded image

Where X is hydrogen or a group selected from the group consisting of cations such as sodium or potassium) These condensation products are available commercially.
It can also be made in the laboratory by conventional methods. Preferred condensation products of this structure, at least 40% of the repeating units comprises a -SO ₃ X groups, at least 40% of the repeat units is a water-soluble product containing the following linking groups.

[0021]

[Chemical 21]

The condensation product should have a molecular weight as high as possible while maintaining some water solubility.
It is good to contain as many monosulfonated phenyl groups as possible. Such products include formaldehyde and the formula:

[0023]

[Chemical formula 22]

[0024]

[Chemical formula 23]

And

[0026]

[Chemical formula 24]

It is conveniently prepared by condensing at high temperature one or more suitable phenols (or derivatives thereof) such as those in an acidic or alkaline medium. Typically in acidic media 0.3 to 0.5 mole formaldehyde is used per mole phenol, and in basic medium 0.9 to 1.5 mole formaldehyde 1 mole.
Used for moles. The solubility of the condensation product in water is affected by the type of end groups present in its structure, hydrophilic groups such as --CH ₂ OH and --CH ₂ SO ₃ H, such as methyl or phenyl groups. Makes the product more water soluble than the group. The basic condensation gives a product with a higher proportion of terminal CH ₂ OH groups and thus greater water solubility.

A polymer condensation product consisting essentially of the above repeating units is a diphenol sulfone having its hydroxyl groups acetylated, then sulfonated and then hydrolyzed to yield acetylated hydroxyl groups as free hydroxyl groups. It can also be produced by a method in which it is converted to the original form and finally reacted with formaldehyde under alkaline or acidic conditions. In this case, the reaction conditions are di- and / or
It is chosen to avoid or at least minimize the formation of products containing tri-sulfonated phenyl groups. In general, the condensation product is repeating unit containing a single -SO ₃ X groups are more effective stain blocking agent than products containing a repeating unit corresponding includes two or more -SO ₃ X group.
Also in general, as the ratio of the units, including one -SO ₃ X group for units that do not contain -SO ₃ X group is increased,
The product becomes a more effective soil barrier.

Condensation products of formula I are commercially available, for example mixed condensation products of phenolsulfonic acid, dihydroxydiphenolsulfone and formaldehyde are available from Ciba-Geigy Corp.
rional) PA under the trade name, or Crompton and Knows
It is available from wles Corp. under the trade name Intratex N.

Also useful as soil barrier agents in the practice of the present invention are mixed condensation products of naphthalene monosulfonic acid, dihydroxydiphenyl sulfone, and formaldehyde. Such a product is commercially available from Ziva Geigy under the trade name Elional NW.

Fluorine compounds useful in the practice of the present invention are applied as a coating to nylon fibers in combination with a soil barrier, and the fluorine compound and soil barrier are 0.35% by weight soil based on the weight of the fiber. When applied in an amount sufficient to provide a coating containing a screener and 650 ppm fluorine and the fibers were used in the manufacture of a carpet, the carpet would produce 3
It is a fluorine compound that remains more resistant to its initial fouling than after the fluorine compound was omitted from the coating, even after exposure to 0,000 passes. Such fluorine compounds include, for example, Minnesota mining
Commercially available under the Scotchgard brand name from And & Manufacturing, Inc. (Scotchguard 358 and 352), and E. I. Included are those commercially available for use on fibers, such as those marketed under the trade names Zepel and Teflon from DuPont de Numer & Co. Typically, these fluorine compounds contain a perfluoroalkyl group (R _f ) having 3 to 20 carbons and are condensation products of R _f OH or R _f NH ₂ with a suitable anhydride or isocyanate, such as , N-ethylperfluorooctyl-sulfonamide ethanol and toluene diisocyanate in a 2: 1 molar ratio.

The nylon fiber coating of the present invention is preferably 0.20 to 0.35% by weight (2000 to
3500ppm) with stain blocker, based on the weight of nylon
Sufficient fluorine compound to give 450-650 ppm fluorine. The soil barrier agent and the fluorine compound may be applied separately or simultaneously. According to a preferred embodiment of the present invention, the soil barrier agent and the fluorine compound are simultaneously applied to the nylon fiber through a finish. According to this embodiment, the antifouling agent and the fluorine compound are of the same polarity, ie both anionic or cationic, in order to avoid the possibility of them precipitating in the finish. The sulfonate-containing soil barrier agents described above are anionic, and therefore it is preferred to use anionic fluorine compounds when using these soil barrier agents. However, it is possible to choose an appropriate dispersant to form a suitably stable finish containing components of opposite charge.

It is possible to select the optimum combination of soil barrier agent and fluorine compound for a particular application from a great variety of soil barrier agents and fluorine compounds, the selected combination being subject to certain conditions. Fine-tuning to give optimum results for a given nylon fiber to which these stain blockers and fluorinated compounds are applied, simply test various combinations of ingredients and find the combination that gives the best results. Selection can be accomplished by routine experimentation within the ability of one of ordinary skill in the art.

Typically, the nylon carpet yarns immediately used for tufting are twin yarn staples or continuous monofilament yarns that have been heat treated to set the twist. The process is called heat setting. Usually, the heat setting operation involves exposing the yarn to steam at about 130-140 ° C, or a Superba device, or about 195 yarn.
This is accomplished using a Suessen device that is exposed to hot air at ~ 205 ° C. Adhesion of the coating to the nylon fibers of the present invention is strengthened by subjecting the coated fibers to Soussen heat setting conditions. The best adhesion of the coating to the fibers is achieved when the coating contains a soil blocking agent having end groups that can further react with the soil blocking agent itself or the surface of the nylon during heat setting. The reaction between the end groups of the dirt blocker and the nylon surface is covalent. Soil barrier agents having such groups include those manufactured under alkaline conditions.

Preferably, the dirt barrier agent and the fluorine compound are 25
4% at temperatures up to ℃, most preferably up to 50 ℃
Fibers having a dye absorption test value of below, most preferably 0 or almost 0 (no visible stain), but at 100 ° C. of at least 30%, most preferably at least 60% Applied to nylon fibers selected to give.

The dye uptake test values given herein are given as% of the dye absorbed by the fiber sample from the red dye No. 40 aqueous solution relative to the temperature of the solution.
The test is conducted as follows.

(1) An aqueous solution of Red Dye No. 40 having a dye concentration of 0.054 g / l is prepared. (This is cherry ...
Red Dye No. 40 concentration in Cherry Cool Aid when a commercial packaged mixture of Cool Aid was mixed with water according to the instructions on the package. ) (2) The light absorption (optical density) of the solution is Cary 15
-Type spectrophotometer or equivalent device, using a 1/2 cm cell, the measurement was performed at 495 mμ, where the red dye No. 40 shows the maximum absorption (light absorption is a measure of the dye concentration of the solution). become).

(3) The light absorption reading is recorded as T ₀ .

(4) Next, 0.25 g of test fiber was placed in a container containing 14.8 ml of Red Dye No. 40 solution, and the pH of the solution was adjusted.
An appropriate amount of universal buffer (Universal Buffe
Adjust to 3 by adding r).

(5) Next, the container is sealed (for example, with a lid),
For example, it is shaken at a temperature selected by a vibrator with a motor for 3 hours, and the temperature is adjusted by a thermostat.

(6) The fibers are then removed from the solution and the light absorption of the solution is measured again as before. (7) Record the reading at this time as T ₁ . (If the fiber sample was not stain resistant, the dye would be taken from the solution and the value of T ₁ would be less than the value of T _0. On the other hand, if the fiber sample was stain resistant. , The value of T ₁ will be the same as or almost the same as the value of T ₀ without taking up too much dye from the solution) (8) The dye absorption test value at the selected temperature is% of the value of T ₀ The dye absorption test value (%) = (T ₀ −T ₁ ) / T ₀ × 100 The following examples are given to further illustrate the present invention.

[0042]

【Example】

Example 1 In this example, nylon 66 fibers of the present invention were prepared and tested to demonstrate their resistance to soiling.

Consisting of 300 monofilaments, one monofilament
60 denier nylon 66 yarn and commercial grade fiber forming nylon 66 are extruded downward through a 300 hole spinner hole at a melting temperature of 282 ° C into a normal spinning tube of about 1.8 m in length. Produced by forming the desired number of melt streams. The spinneret was used to undergo ambient temperature cooling air cross flow at a rate of 270 m / min. The melt stream solidified in the spinning tube to form single fibers. The monofilaments were passed from the spinning tube through a conventional steam conditioning tube about 1.8 m long, where they were treated with steam. The monofilaments are sent from the conditioning tube to a conventional metering and finisher applicator where they contain a soil blocker and a fluorine compound in amounts sufficient to provide 3500 ppm soil blocker and 650 ppm fluorine, respectively, based on the weight of the fiber. An aqueous finish was applied and the single fibers were bundled to form a yarn. Next, the yarn is driven and supplied (driving speed 450 m /
Min) and a separator roll attached to it and wound several times. The yarn was then wound onto the bobbin with slight tension to help the yarn to be wound on the bobbin. The yarn was then unwound from the bobbin and combined with 54 similar yarns, all denier forming about 1,000,000 tows. Stretch the tow on a roll and nominally 18 dp
Tows of f (denier per filament) were obtained, crushed in a conventional packing box and cut into 71/2 inch staples. Carding staples, drafting, spinning with a normal ring spinning machine, 1 in Z direction
Approximately 177 times per m (177 tpm [4.5 times per inch (4.5 tpi)])
A 31/2 count single yarn having a twist of 3 was obtained.
Two of these yarns were then twisted together in the S direction with a 157 tpm (4.0 tpi) twist. A portion of the twisted yarns were heat set at 200 ° C. using normal Susen heat setting conditions.

The stain blocker (stain blocker A) used to make the heat-set and non-heat-set yarns described above consists essentially of repeating units of the formula:

[0045]

[Chemical 25]

And R'is at least 50% of the units --S
O ₃ Na, hydrogen in the remaining units. The fluorine compound used to make these yarns was a mixture of anionic fluorine compounds based on N-ethyl-perfluorooctyl-sulfonamidoethanol.

Dye absorption test values for samples of heat-set yarn (Yarn E) and non-heat-set yarn (Yarn D) were determined at the various temperatures shown in Table I below. The heat-set yarn is represented by curve E in FIG. 1, and the non-heat-set yarn is represented by curve D. ) Both yarn E and yarn D are considered to be within the scope of the present invention. In another experiment, heat-set and unheat-set yarns (controls) were prepared in the same manner as described above, except that the soil barrier and fluorine compounds were omitted from the finish. It was Dye absorption test values for a sample of the unheated control yarn (Yarn A) were determined and are shown in Table I. (This yarn is represented by curve A in Figure 1.) A sample of heat set control yarn (conventional nylon carpet yarn) was tested in accordance with the teachings of U.S. Pat. No. 3,118,723 with 2% by weight acetic acid and 0.5% by weight. Immerse in an aqueous bath containing Elional NW, then boil the bath for 20 minutes, keep the bath boiling for another hour, remove the yarn from the bath, then wash and dry the yarn Processed by. Dye absorption test values for this yarn (Yarn B) were determined and are also shown in Table I. (This yarn is represented by curve B in FIG. 1.) This treatment of yarn is a beck of the carpet.
It mimics the treatment of carpet in which Elional NW is added to the dyebath as a dyeing aid (leveling or anti-dye) in dyeing.

Second Control Yarn Not Heat Set
Sample was also processed in the manner just described, following the teaching of US Pat. No. 3,118,723 (Example I thereof). The treated sample was then heat set by heating the sample in a 200 ° C. air atmosphere for 1 minute and then cooled to ambient temperature. Dye absorption test values for this treated and heat set yarn (Yarn C) were determined and are also shown in Table I below. (This yarn is represented by curve C in Figure 1). Yarn C is considered to be a yarn that falls within the scope of the present invention.
This treatment of the sample differs from the above treatment (conventional method) in that the sample is treated and then heat set.
On the other hand, in the above example, the sample has been heat set and then processed.

FIG. 1 is a plot of the data given in Table 1. Curves A, B and C in FIG. 1 each end at a point defined by the intersection of the coordinates of 100 ° C. and 100%.

[0050]

[Table 1]

The data shown in Table 1 and shown in FIG. 1 clearly show the exceptionally stain resistant property of the nylon fiber of the present invention as compared with the conventional nylon fiber. Looking at FIG. 1, the fibers represented by curves A and B are
Each of them was stained to a bright red color at 25 ° C and did not have a significant stain resistance property. The fibers represented by curve C (invention) stain light pink at 25 ° C and are barely acceptable for some carpet yarn applications, but nevertheless the fibers represented by curves A and B. It was much harder to get dirty. Curves D and E
It is worth noting that the fibers represented by were not soiled at 25 ° C at all.

Example 2 This example illustrates the unexpected advantages obtained by coating nylon fibers with a fluorine compound and a stain barrier. This example shows that carpets made from these fibers have a greater degree of resistance to initial stains after passage than do comparable carpets made from nylon fibers coated only with dirt barrier. Shows that it keeps.

Thirteen nylon 66 yarns consisting of 68 monofilaments and having a denier (dpf) of 60 per filament were produced. Each yarn is made of commercial grade fiber forming nylon 66 with a melting temperature of 274
It was prepared by extruding downwards through a 68-hole spinneret hole at 68 ° C. into a conventional spinning cylinder about 1.8 m long to form a corresponding number of melt streams. The spinneret was used to undergo a cross flow of 18.3 ° C. cooling air at a flow rate of 11.2 l / min. The melt stream solidified in the spinneret to form monofilaments. The monofilaments were passed from the spinning tube through a conventional steam conditioning tube about 1.8 m long, where they were treated with steam. The monofilaments were sent from the conditioning tube to a conventional metering finish application device where an aqueous finish containing soil barrier and / or fluorine compounds was applied. The stain blocker used in this example was Elional PA.
And the fluorine compound was Scotchguard FC358. The amounts of soil blocker and fluorine compound were varied from yarn to yarn, as shown in Table 2. Two of these yarns were twisted together as described in the examples and then stretch-filamented on a draw-filament machine to give fibers of about 18 dpf. The obtained double yarn was heat set by a Susen heat setting device (200 ° C. for 1 minute). Two sets of similar samples were obtained with those yarns. 13 of each of those samples
Included were strips, each strip tufted with a different yarn. The 26 strips obtained were made into 2.5% by weight [of product weight (owg)] calgon.
(Calgon) and 1.0 wt% owg of Alkanol
Fabric dyeing was performed using a solution of ND and 2.0 wt% owg of ammonium sulphate at a solution: article weight ratio of 40: 1. The strips and solution were then heated to boiling for 55 minutes and kept boiling for another 60 minutes with stirring. The solution was removed. The strips were then rinsed 3 times with water, rollerd after each rinse to allow 200% water uptake in each rinse and finally dried at ambient conditions for 48 hours.

A set of fabric dyed strips was tested to determine the initial stain resistance of the various strips. The test consisted of applying to the surface of each strip 3 drops of an aqueous solution of Red Dye No. 40 at a concentration of 0.054 g / l. (0.054 g / l is the concentration of Red Dye No. 40 in Cherry Cool-Aid.) The solution was applied to the strip by applying pressure with a spatula. Red stains formed on each strip. (10 spatula
Reciprocating between 20 and 20 times is usually sufficient to ensure that the fiber penetrates the solution. ) Each strip was then processed as follows. An additional 7 drops of solution was applied to the stain, rubbed with a spatula and left for 10 minutes. After 10 minutes, the stain was blotted off with a paper towel until no more solution could be drained off. The stain was then dried for 16 hours. Each strip was then cleaned as follows. 4 ml of carpet cleaning solution was applied to the stain. 28.4g of steam clean (St
eam Clean) 300PG [Procter & Gamble Company
(Commercially available from (Procter and Ganble Co)]
It was made by adding to 473 ml deionized water. The cleaning solution was left on the stain for 30 seconds and then blotted dry with a paper towel. Then 4 ml of vinegar (5% acetic acid in deionized water) was applied to the stain and left in contact with the stain for 30 seconds. After 30 seconds, the stain was absorbed and dried. Then 4 ml of carpet cleaner was applied to the stain, left for 30 seconds, then blotted dry. Finally 10 ml of deionized water was applied to the blot and the blot was blotted dry. The strips were then compared to 6 strips presoiled with Red Die No. 40 to various stain levels ranging from unstained (1) to completely soiled (6). In this case, the difference in color between adjacent stains was almost the same. The strips were mounted on a plate and the test strips were aligned with the strips on the plate and their numbers were determined. 1 if less than 2
A decimal scale was used to indicate the approximate value between 2 and 2. Strips rated 2 or higher were judged to have no significant stain resistance and therefore failed the test. Floor test the second set of selected strips for 30,000 passes and then the stain resistance test above, if any, if the passage (wear) is to the first stain resistance of the strip. I investigated what kind of effect it would have on them. Table 2 shows the test results before and after passage.

[0055]

[Table 2]

FIG. 2 is a plot of the data shown in Table 2. In FIG. 2, the dirt grade numbers not enclosed in parentheses were obtained before the passage (*), and those in parentheses were obtained after the passage (**).

The results given in Table 2 and shown in FIG. 2 show that nylon fibers coated with a blocking spinner and a fluorocompound (eg 2D3) are better than the corresponding fibers without the fluorocompound (2D1). , Shows that it retains a greater degree of resistance to those initial stains after passage. These results show the effect of soil blocker and fluorine compound concentrations on soil susceptibility.

Example 3 In this example, nylon fibers were coated with a fluorine compound or a stain barrier or a combination thereof and then tested for stain resistance.

A twisted yarn was prepared as described in Example 1. However, in one example, the stain blocking agent A and the fluorine compound are not included (control yarn), and in another example, the finish agent includes the stain blocking agent A but no fluorine compound (SB yarn). In another example, the finish contained a fluorine compound but no stain barrier (FC yarn), and in yet another example, the finish contained both stain barrier A and a fluorine compound ( S. B. + F. C. yarn). The fluorine compound used in this example was the same as that used to make the yarn described in Example 1.

The stain blocker and fluorine compound, when present in the finish, are present in an amount sufficient to provide 3500 ppm of stain blocker and 650 ppm of fluorine to the yarn, based on the weight of the yarn. It was All yarns were heat set at 200 ° C using normal Susen heat setting conditions. Dye absorption test values for samples of each yarn were determined at 30 ° C and 100 ° C and are shown in the following table.

[0061]

[Table 3]

The results in Table 3 show that the fluorine compound itself does not impart significant stain resistance to nylon fibers. These results further indicate that the use of a fluorine compound in conjunction with a soil barrier did not improve the soil resistance of the soil barrier, thereby increasing the value of the combination after the initial soil resistance. It is possible to confirm the result given in Example 2 that the durability is also maintained, that is, durability is maintained.

Example 4 Two 31/2 count single yarns were prepared as described in Example 1. However, in this case the dirt barrier was Intralatex N and the yarns were not individually heat set. No fluorine compound was used. The yarn was twisted by 118 tpm (3 tpi) in the S direction with an ordinary ring twisting machine. The twisted yarn obtained is then
Heat set at 200 ° C. using Soussen heat set conditions. A cut pile tufted carpet sample was made from heat set twisted staple yarn and dyed in a bright gold color. Light gold was chosen as a color that contrasts well with most stains.

The carpet samples were exposed to the common household liquid materials listed in the table below to determine the resistance of the samples to stains from the colorants present in these materials. Apply each substance to the carpet sample, rub it onto the carpet, leave it on the sample overnight, and finally on the next day wash the sample first with a dilute aqueous solution of a commercial detergent and then with water to remove the substance. Removed. For comparison purposes, a carpet sample (control) was made in the manner described above. However, in this case the yarns from which these samples were made were not treated with Intralatex N. That is, Intralatex N was omitted from the finish.

[0065]

[Table 4]

The results shown in the table show that while the nylon fibers treated according to the invention have excellent stain resistance,
The corresponding fibers not so treated clearly show a lack of stain resistance.

The exposed cut ends of pile fibers of carpet samples made from the fibers of the invention are stain resistant, indicating that the stain blocker not only coats the surface of the fibers but also penetrates the fibers. .

Example 5 Of the contaminants tested in Example 4, the most severely soiled untreated carpet (control) was the soft drink containing Red Dye No. 40 (Cherry Cool Aid). Another test was then conducted to investigate the effect of spilling a large amount of soft drink on a carpet sample made from the nylon 66 fiber of the present invention. 3785 ml (1
Gallons) soft drink was poured from a 1 gallon milk container onto the carpet sample. The container was held 1 meter above the surface of the carpet sample. The concentration of the dye in the soft drink was 0.054 g / l. The carpet sample was made in the manner described in Example 2. However, half of the samples were made from yarns with fibers treated with Intralatex N, and the other half (control) were made from corresponding yarns with fibers not treated with Intralatex N. The soft drink was poured on both halves of the carpet sample from a distance of about 1 meter above the carpet sample so that the same amount was poured on each half of the carpet sample. The soft drink was left on the sample overnight and no steps were taken to clean the carpet or remove the soft drink until the next day. The next day the carpet samples were cleaned in the manner described above. Surprisingly after cleaning, soft drinks (Red Dye No. 4
No trace of 0) remained on one half of the carpet sample made from the inventive fibers, while the other half of the carpet sample was heavily soiled.

Similar results were obtained using the soil barrier agents used in Examples 1 and 2 in place of the soil barrier agents used in this example.

Example 6 In this example two nylon carpet yarns were produced,
One made according to the invention (dirt barrier yarn) and one made according to the state of the art (control yarn). The yarns were then similarly treated to make cut pile carpets, respectively. Both carpets were identical except one was made with the soil barrier yarn and the other with the control yarn. The carpets were then tested for dirt resistance before and after passing.

The yarn of the present invention (dirt barrier yarn) was made by the following method.

Nylon 66 consisting of 300 monofilaments and 60 denier (60 dpf) per monofilament was melted at a melting temperature of 282 ° C.
It was prepared by extruding downward through a 00-hole spinneret into a conventional spinning cylinder about 1.8 m long to form a corresponding number of melt streams. The spinneret was used to undergo ambient temperature cooling air cross flow at a rate of 270 m / min. The melt stream solidified in the spinning tube to form single fibers. The monofilaments were passed from the spinning tube through a conventional steam conditioner tube about 1.2 m long where they were treated with steam. The monofilaments are sent from the conditioner tube to a conventional metering and finishing device, where they contain a soil blocker and a fluorine compound in amounts sufficient to provide 3500 ppm of stain blocker and 650 ppm of fluorine, respectively, based on the weight of the fiber. An aqueous finish was applied and the single fibers were bundled to form a yarn. The yarn was then fed several times around a drive feed roll (450 m / min) and its associated separator roll. The yarn was then wound onto the bobbin with slight tension to help the yarn to be wound on the bobbin. The yarn is then unwound from the bobbin and combined with 54 similar yarns with a total denier of about 1,
Formed a million tows. Draw the tow on a roll,
Nominally 18 dpf (denier per filament) tow was obtained, which was chopped in a conventional packing box and cut into 19.05 cm (71/2 inch) staples. Carding and drafting staples, spinning with a conventional ring spinning machine,
Approximately 177 times per meter in the Z direction (177 tpm) [per inch]
4.5 times (4.5 tpi)] with a 31/2 count single yarn. Two of these yarns were then twisted together in the S direction with a 157 tpm (4.0 tpi) twist. The stain blocker and fluorine compounds used to make this yarn were the same as those used to make the yarn described in Example 1.

A control yarn was made in the same manner as just described. However, the stain blocking agent and the fluorine compound were omitted from the finish.

Both yarns were heat set at 200 ° C. using a conventional Susen heat set. Saxony (sa
A xony) construction carpet was made from each yarn. Each yarn has 27.6 stitches per 10 cm (stitch per inch)
Then, I tufted with a 5/32 gauge cut pile tufting machine for the primary backing. The height of the pile is 2.2 cm
(7/8 inch) per square yard of carpet
A 32 ounce yarn was used. Each carpet is beck (be
ck) in a light beige dyeing. The secondary backing was glued to the primary backing. Each carpet was subjected to the following tests.

Each carpet sample was tested to determine its resistance to Red Die No. 40 before passing.
An aqueous solution of the dye was prepared at a concentration of 0.054 g / l as described in Example 4 and used for testing carpet samples. Inner diameter
Five 2.54 cm, 10 cm long open cylinders were placed vertically on each carpet sample. 20 ml of Red Dye No. 40 solution was injected into each cylinder at the time intervals shown below: cylinder at t ₀ (start) 1 t ₀ +2 hours cylinder 2 t ₀ +4 hours cylinder 3 t ₀ +6 hours cylinder Cylinders at 4 t ₀ +7 h After 58 h (t ₀ +8), all cylinders were removed from the carpet sample and the stains were blotted with paper towels to remove excess solution. Then 1 of those stains on each carpet sample
Graded on a scale of ~ 8. 1 is a heavily soiled carpet and 8 is the case with no visible soiling on the carpet. Red Die No.40 for each carpet sample
The solution was contacted for 1, 2, 4, 6 and 8 hours. Each time corresponds to one of the stains on the carpet sample. The test results are shown in Table 5.

[0076]

[Table 5]

A second sample of each carpet was exposed to 128,000 passes and then tested in the manner just described. The results of this test are shown in Table 6.

[0078]

[Table 6]

FIG. 3 is a photograph of a carpet made from dirt barrier yarn (invention) before passage and after a dirt test. FIG. 4 is a photograph of a carpet made from control yarns before passage and after a soil test. FIG. 5 is a photograph of a carpet made from the dirt barrier yarn (invention) after first being exposed to 128,000 passes and then subjected to a dirt test. Sixth
The figure is a photograph of a control yarn after it was first exposed to 128,000 passes and then subjected to a stain test.

Each photograph is a photograph of the aforementioned cut pile carpet sample. Each tuft of carpet was made from nylon yarn. Each carpet was exposed to Red Die No. 40 for 1, 2, 4, 6 and 8 hours. Each photo was taken at a size of 1 / 2.67 under the same conditions. The yarns in each carpet were such that the fibers of the yarns used to make the carpet shown in FIGS. 3 and 5 were coated according to the present invention and the carpets shown in FIGS. 4 and 6 were used. The yarn used to make the loop (control) is similar except that it is not.

The results shown in Tables 5 and 6 and shown in Figures 3-6 clearly demonstrate the exceptional and advantageous stain resistant properties of the fibers of the present invention. In FIGS. 3 and 4, the word “first” means before the passage, and in FIGS.
In the figure, the word "dirty" means after traffic. The results show that the fibers coated according to the invention are virtually unfouled with respect to Red Die No. 40 even after 128,000 passes, whereas omitting the coating from the fibers results in the fibers being effectively dyed. It indicates that you will not be protected. It is noteworthy that carpets made from the fibers of the present invention do not stain at all before passage and very little stain after passage even when the dye is in contact with the carpet for up to 8 hours. . This would be the case, for example, if the child spilled the soft drink and did not notice that it spilled for a long time. Such events are not uncommon in a typical home.

[Brief description of drawings]

FIG. 1 is a plot showing the influence of temperature on the dye absorption test value of the nylon fiber of the present invention and the conventional nylon fiber.

FIG. 2 is a plot showing the effect of a soil blocking agent and a fluorine compound on the soil resistance of nylon fibers before passage.

FIG. 3 is a photograph of a carpet (fiber form) made from a stain barrier yarn (invention) before passing and after having been subjected to a stain test.

FIG. 4 is a photograph of a carpet (fiber form) made from a control yarn before passing and after having been subjected to a soil test.

FIG. 5 is a photograph of a carpet (fiber form) made from a soil barrier yarn (invention) after first being exposed to 128,000 passes and then subjected to a soil test.

FIG. 6 is a photograph of a control yarn (fiber form) after first exposure to 128,000 passes and then a stain test.

Claims (16)

[Claims] 1. A coating having one or more stain-blocking agents on its surface, a dye absorption test value at 25 ° C. of almost 0, and a dye absorption test value at 100 ° C. of 30% or more. A non-staining nylon fiber, wherein the stain-blocking agent is (a) essentially the following repeating unit: [However, R is a group which may be the same or different for each unit, and is hydrogen, —SO ₃ X, or And (Where X is hydrogen or a cation). And at least 40% of the repeating units contain a —SO ₃ X group, and at least 40% of the repeating units have the following bonds: An undyed stain-resistant nylon fiber selected from a condensation polymer product containing (b) and a mixed condensation product of (b) naphthalene monosulfonic acid, dihydroxydiphenyl sulfone and formaldehyde. 2. The nylon is nylon 66.
The fiber according to claim 1. 3. The fiber of claim 1 wherein the fiber has a denier in the range of 8 to 24. 4. The fiber according to claim 3, which has a staple shape. 5. The fiber according to claim 3, which is in the form of continuous single fiber. 6. The fiber according to claim 1, wherein the dye absorption test value is in a range represented by a region above the curve E and below the curve C in FIG. . 7. The fiber according to claim 1, wherein the dye absorption test value is in a range represented by a region above the curve E and below the curve D in FIG. . 8. The fiber according to claim 1, wherein the stain blocking agent is a mixed condensation product of phenolsulfonic acid, dihydroxydiphenolsulfone and formaldehyde. 9. The fiber according to claim 1, wherein the stain blocking agent is a mixed condensation product of naphthalene monosulfonic acid, dihydroxydiphenyl sulfone and formaldehyde. 10. A coating having one or more stain-blocking agents on its surface, a dye absorption test value at 25 ° C. of almost 0, and a dye absorption test value at 100 ° C. of 30% or more. A stain-resistant nylon fiber, wherein the stain-blocking agent is (a) essentially the following repeating unit: [Wherein R is a group which may be the same or different for each unit, and is hydrogen, —SO ₃ X, or And (Where X is hydrogen or a cation). And at least 40% of the repeating units contain a —SO ₃ X group, and at least 40% of the repeating units have the following bonds: embedded image A yarn made of a nylon fiber which is resistant to stain, which is selected from the group consisting of a condensation polymer product containing: and (b) a mixed condensation product of naphthalene monosulfonic acid, dihydroxydiphenyl sulfone and formaldehyde. 11. The pile has essentially the following nylon fibers, ie: a coating containing one or more stain-blocking agents on its surface, and a dye absorption test value at 25 ° C. of almost zero. A stain resistant nylon fiber having a dye absorption test value of 30% or more at 100 ° C., wherein the stain blocking agent is (a) essentially the following repeating unit: [Wherein R is a group which may be the same or different for each unit, and is hydrogen, —SO ₃ X, or And (Where X is hydrogen or a cation). And at least 40% of the repeating units contain a —SO ₃ X group, and at least 40% of the repeating units have the following bonds: A carpet made of stain-resistant nylon fiber, which is selected from the group consisting of a condensation polymer product containing: and (b) a mixed condensation product of naphthalene monosulfonic acid, dihydroxydiphenyl sulfone and formaldehyde. 12. The carpet according to claim 11, wherein the carpet has a cut pile structure. 13. A coating having one or more stain-blocking agents on its surface, a dye absorption test value at 25 ° C. of almost 0, and a dye absorption test value at 100 ° C. of 30% or more. A method for producing a nylon fiber which is less likely to be soiled, wherein in the melt spinning step in which the nylon fiber is produced,
Or the step of applying a spin finish containing more stain-blocking agents to the nylon fibers, and wherein the stain-blocking agent comprises (a) essentially the following repeating units: [Wherein R is a group which may be the same or different for each unit, and is hydrogen, —SO ₃ X, or And (Where X is hydrogen or a cation). And at least 40% of the repeating units contain a —SO ₃ X group, and at least 40% of the repeating units have the following bonds: A method for producing a stain-resistant nylon fiber, which is selected from a condensation polymer product containing: and (b) a mixed condensation product of naphthalene monosulfonic acid, dihydroxydiphenyl sulfone and formaldehyde. 14. The nylon according to claim 1, which is nylon 66.
The method according to 3. 15. The method according to claim 13, wherein the stain blocking agent is a mixed condensation product of phenolsulfonic acid, dihydroxydiphenolsulfone and formaldehyde. 16. The method according to claim 13, wherein the stain blocking agent is a mixed condensation product of naphthalene monosulfonic acid, dihydroxydiphenyl sulfone and formaldehyde.