JP2537601B2 - Stain-resistant nylon fiber - Google Patents

Description

Description: BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to nylon fibers having exceptional and advantageous dyeing properties. In particular, the present invention relates to a nylon fiber that is less susceptible to stains by acid dyes at ambient temperature, but can be dyed at high temperature without losing stain resistance by acid dyes at ambient temperature. Normal nylon fiber is
It can be permanently soiled at room temperature by acid dye colorants commonly found in household items such as drinks, foods, cosmetics, pharmaceuticals, and parties. 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 "dirty" as used herein with respect to nylon fibers means the discoloration of the fibers caused by the chemical reaction of a compound such as an acid dye with the nylon fibers.

"Conventional" Nylon fiber carpets are a common floor covering in both residential and commercial applications. Such carpets are relatively inexpensive and provide the desired combination of properties such as durability, aesthetics, comfort, safety, warmth and sound deadening. Also, various attractive colors,
You can get patterns and textures. However, nylon fibers are severely and permanently soiled by some of the artificial and natural colorants present in common household items such as Kool Aid and other soft drink beverages, which is why they are made from nylon fibers. The resulting carpet is easily damaged by the spilling of such items. Most of these colorants are acid dyes, all of which are accepted by the Food, Medicine and Cosmetics Commission for human consumption. One of the most commonly used acid dye colorants that stains nylon most severely at room temperature is FD & C Red Dey No. 40 (hereinafter "Red Dye No. 40"). Red Die No.40
(Also known as CTFood Red 17) has the following structure; 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. 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, these fibers are dyed within minutes by their colorants and are therefore permanently soiled.

Looking over the carpet replacement market, we see that more carpet is being 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.

SUMMARY OF THE INVENTION The present invention is not susceptible to fouling by acid dye colorants at ambient temperatures, but is acidic in the conventional manner at elevated temperatures without loss of stain resistance to the acid dye colorants at ambient temperature. Gives a nylon fiber that can be dyed with a dye. The nylon fibers of the present invention have one or more stain blockers (Stain blockers) in an amount sufficient to provide fibers having a "dye absorption test value" of 7% or less at 25 ° C and 30% or more at 100 ° C as defined later. ) Is included on the surface.

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 and 100 ° C. Means a compound that gives a fiber of 30% or more.

The fibers of the present 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 is exposed to one or more stain-blocking agents and one or more fluorine compounds for 30,000 passes when the fibers are used in the manufacture of carpets. Even after that, the fluorinated compound is included in an amount sufficient to provide the carpet with a carpet that retains a greater degree of initial dirt resistance of the carpet than would be the case in the corresponding carpet. 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). It doesn't even give to the former). 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.

Preferred Embodiments Any nylon fiber may be coated according to the present invention. Nylon fibers of commercial interest are fibers formed from nylon 66 (polyhexamethylene adipamide) and nylon 6 (polycaprolactum). The present invention is particularly useful in providing Nairro carpet yarns that can be made into stain resistant carpets. 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.

Particularly useful soil barrier agents in the practice of the present invention include, for example, condensation polymer products consisting essentially of repeating units of the formula: (In the formula, R is the same or different in each unit, hydrogen or
SO ₃ X, (Wherein X is hydrogen or a cation such as sodium or potassium) selected from the group consisting of :) These condensation products can be obtained as commercial products, or in the laboratory. It can be made by the usual method. 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 an aqueous product containing the following linking groups.

The condensation product should have as high a molecular weight as possible while maintaining some water solubility while containing as many monosulfonated phenyl groups as possible. Such products include formaldehyde and the formula: and, One or more suitable phenols (or their derivatives) such as
It is conveniently produced by condensing and in an acidic or alkaline medium at high temperature. Typically in acidic media 0.3 to 0.5 moles of formaldehyde are used per mole of phenol and in basic media 0.9 to 1.5 moles of formaldehyde are used per mole of phenol. The solubility of the condensation product in water is influenced by the type of end groups present in its structure, for example -CH.
Hydrophilic groups such as ₂ OH and -CH ₂ SO ₃ H make the product more water soluble than groups such as methyl or phenyl groups. Due to the basic condensation, the proportion of terminal CH ₂ OH groups is larger,
Therefore, a product having a higher solubility in water is provided.

A polymer condensation product consisting essentially of the above repeating units is obtained by acetylating diphenol sulfone after its hydroxyl group is sulfonated and then hydrolyzed to convert the acetylated hydroxyl group to a free hydroxyl group. It can also be produced by a method of returning to the original state and finally reacting with formaldehyde under alkaline or acidic conditions. In this case, the reaction conditions are selected to avoid or at least minimize the formation of products containing di- and / or 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, -SO ₃ X
As the ratio of units containing one —SO ₃ X group to units containing no groups increases, the product becomes a more effective stain blocker.

Condensation products of formula I are commercially available, for example a mixed condensation product of phenolsulfonic acid, dihydroxydiphenolsulfone and formaldehyde is available from Ciba-Geigy Corp.
l) Available under the trade name PA, or Crompton and Knowles
Corp.) under the trade name Intratex N.

Also useful as soil barrier agents in practicing 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 based on the weight of the fiber.
When applied in an amount sufficient to give a coating containing 0.35% by weight of a stain blocker and 650 ppm of fluorine and the fibers were used in the manufacture of a carpet, the carpet remained exposed after 30,000 passes. , A fluorine compound that maintains its initial dirt resistance to a greater extent than if the fluorine compound were omitted from the coating. Such fluorine compounds include, for example, Scotchgard (Soctchgar) from Minnesota Mining and Manufacturing.
d) Commercially available under the brand name (Scotchguard 358
And 352), and those marketed for use with fibers, such as those marketed under the trade names Zepel and Teflon from EI 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-
It is the reaction product of ethyl perfluorooctyl-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 wt% (2000 to 3500 ppm) based on the weight of the nylon.
450-650 pp based on the weight of nylon
Sufficient fluorine compound to give m 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 most suitable combination of soil barrier agent and fluorine compound for a particular application from a wide variety of soil barrier agents and fluorine compounds, and the selected combination is Fine-tuning to give optimum results for a given nylon fiber to which a soil blocker and a fluorine compound are applied is to simply test various combinations of ingredients and select the combination that gives the best results. 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 yat. Typically, the heat yat operation is accomplished using a Superba device that exposes the yarn to steam at about 130-140 ° C or a Suessen device that exposes the yarn to hot air at about 195-205 ° C. The adhesion of the coating to the nylon fiber of the present invention is
It becomes strong 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. Anti-aliasing agents having such groups include those manufactured under alkaline conditions.

Preferably the stain blocker and the fluorine compound have a dye uptake of less than 4%, most preferably 0 or almost 0 (no visible stain) at temperatures up to 25 ° C, most preferably up to 50 ° C. Has test value, but at least 30 at 100 ° C
%, Most preferably applied to nylon fibers selected to give fibers having a dye absorption test value of at least 60%.

The dye absorption test values given here are Red Dye N
Given as a percentage of the dye absorbed by the fiber sample from the solution to the temperature of the o.40 aqueous solution. The test is conducted as follows.

(1) Red dye No. 40 with a dye concentration of 0.054 g /
An aqueous solution of is prepared. (This is the concentration of Red Dye No. 40 in Cherry Cool Aid when a commercially available packaged mixture of Cherry Cool Aid was mixed with water according to the instructions on the package.) (2) Solution Light absorption (optical density) is Cary
Type 15 spectrophotometer or equivalent device was used to measure with a 1/2 cm cell, and the measurement was carried out at 495 mμ where the red dye No. 40 shows the maximum absorption. Will be a guide for).

(3) Record the light absorption reading as T ₀ .

(4) Next, add 0.25 g of test fiber to 14.8 ml of Red Dye N.
Place in a container containing o.40 solution and adjust the pH of the solution to 3 by adding the appropriate amount of Universal Buffer.

(5) The container is then sealed (eg, capped) and shaken, for example, with a motorized vibrator at a selected temperature for 3 hours, and the temperature is adjusted with 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 T ₁ value would be less than the T ₀ value.
On the other hand, if the fiber sample is not easily soiled, 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) Selected temperature The dye absorption test value is expressed in% of the value of T ₀ and calculated as follows: Dye absorption test value (%) = (T ₀ −T ₁ ) / T ₀ × 100 Is given to explain further.

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

Nylon 66 yarn consisting of 300 single fibers, 60 denier per single fiber, commercial grade nylon 66 for fiber formation
Through a 300-hole spinneret hole with a melting temperature of 282 ° C.
It was prepared by extruding downwards into a conventional spinning cylinder 8 m long to form a corresponding number of melt streams. The spinneret was used to receive the ambient temperature cooling air flowing crosswise at a velocity of 270 m / min. The melt stream solidified in the spinning tube to form single fibers. These filaments are approximately
It was passed through a 1.8 m conventional steam conditioning tube where the monofilaments were steamed. The single fibers are sent from the conditioning tube to a conventional metering agent applicator where they contain a stain blocker and a fluorine compound in amounts sufficient to provide 3500 ppm stain 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. The yarn was then fed to a drive supply roll (drive speed 450 m / min) and its associated separator roll and wound several times. The yarn was then wound onto a bonbin 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. The tow was drawn on a roll to give a nominal 18 dpf (denier per filament) tow, which was chopped in a conventional filling box,
It was cut into 19.05 cm (71/2 inch) staples. The staples are carded, drafted, and spun by a normal ring spinning machine, and about 177 times per 1 m in the Z direction (177 tpm
A 31/2 th single yarn having a twist of [4.5 times per inch (4.5 tpi)] was obtained. Two of these yarns were twisted in the S direction next to 157 tpm (4.0 tpi) and twisted together. A portion of the twisted yarns were heat set at 200 ° C. using normal Soussen heat setting conditions.

The soil barrier agent (rice soil barrier agent A) used to make the heat-set and non-heat-set yarns described above consists essentially of repeating units of the formula: And R 'is -SO ₃ Na in at least 50% of the units,
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 various temperatures shown in Table 1 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 control yarn that was not heat set (Yarn A) were determined and are shown in Table 1. (This yarn is represented by curve A in FIG. 1.) A sample of the heat set control yarn (conventional nylon carpet yarn) was tested in accordance with the teachings of US 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. The dye absorption test values for this yarn (Yarn B) were determined and are also shown in Table 1. (This yarn is represented by curve B in FIG. 1.) This treatment of yarn is based on the bec of the carpet.
k) It mimics the treatment of carpet in which Elional NW is added to the dyebath as a dyeing aid (leveling agent or anti-dye) in dyeing.

A second sample of control yarn that was not heat set was also processed in the manner just described according to the teachings 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 1 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.
It ends at the point defined by the intersection of the coordinates of ° C and 100%.

The data shown in Table 1 and shown in FIG. 1 clearly show the exceptional stain resistance of the nylon fibers of the present invention as compared to conventional nylon fibers. Looking at FIG. 1, the fibers represented by curves A and B are 25
It was stained to a bright red color at 0 ° C and did not have a significant stain-resistant 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. It is worth noting that the fibers represented by curves D and E did not stain 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.

Denier (dpf) per single fiber consisting of 68 single fibers
Produced 13 nylon 66 yarns of 60. Each yarn extruded commercial grade fiber-forming nylon 66 downwards through a 68-hole spinneret at a melt temperature of 274 ° C. into a conventional spinning barrel of about 1.8 m in length, producing a corresponding number of melt streams. Manufactured by forming. The spinning cylinder contains 11.3m3 / cooling air at 18.3 ℃.
Used to undergo cross flow at minute flow rates.
The melt stream solidified in the spinneret to form monofilaments. The monofilaments were passed from a 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 soil barrier used in this example was Elional PA and the fluorine compound was Scotchgard FC358. The amount of soil blocker and fluorine compound was varied from yarn to yarn as shown in Table II. Two of these yarns were twisted together as described in the Examples and then drawn-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 (20
0 ° C for 1 minute). Two sets of similar samples were obtained with those yarns. Each of the samples contained 13 strips, each strip being tufted with a different yarn. Twenty-six strips obtained were treated with 2.5% by weight [owg] [Calgon] of 1.0
Alkanol ND at wt% owg and 2.0 wt% o
Fabric dyeing was performed with a solution of wg 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 /. (0.05
4g / is Red Die No.40 in Cherry Cool Aid
Is the concentration of ) The solution was applied to the strip by applying pressure with a spatula. Red stains formed on each strip. (A 10 to 20 round trip of the spatula is usually sufficient to ensure that the fiber is infiltrated with the solution.) Each strip was then treated 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 Steam Clean 300P cleaning solution in advance
G [Procter and Ganbl
e.g., a product commercially available from e Co)] was added to 473 ml of 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% in deionized water
Acetic acid) 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 pre-soaked with Red Die No. 40 to varying degrees of soiling ranging from unsoiled (1) to fully soiled (6). In this case, the difference in color between adjacent stains was almost the same. Attach these strips on the board,
The test strip was fitted to the strip on the board and its number was determined. For numbers less than 2, decimal point grades were used to indicate approximate values between 1 and 2. Strips rated 2 or higher were judged to have no significant stain resistance and therefore failed the test. For the second set of selected strips
Floor test for 30,000 passages, then the stain resistance test above, if any, to see how passage (wear) affects the initial stain resistance of the strip. It was Second test results before and after traffic
Shown in the table.

FIG. 2 is a plot of the data shown in Table 2. In FIG. 2, the stain 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 Figure 2 show that nylon fibers coated with a blocking spinner and a fluorine compound (eg 2D
3) shows that it retains a greater degree of resistance to their first stain after passage than the corresponding fibers (2D1) with the fluorinated compound omitted. 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 finishing agent includes the stain blocking agent A but no fluorine compound (SB yarn), and yet another example. In the example, the finishing agent contained a fluorine compound but did not contain the stain blocking agent (FC yarn), and in yet another example, the finishing agent contained both the stain blocking agent A and a fluorine compound (SB + FC 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, were present in amounts sufficient to provide 3500 ppm of stain blocker and 650 ppm of fluorine to the yarn, based on the weight of the yarn. 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.

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 th 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 in a S direction with a conventional ring twisting machine by twisting at 118 tpm (3 tpi). 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 and the resistance of the samples to stains from the colorants present in these materials was determined. 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.

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

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

Example 5 Of the pollutants tested in Example 4, the most severely soiled untreated carpet (control) was Red Dye No. 4.
It was a soft drink containing 0 (cherry cool aid). Another test was then conducted to investigate the effect of spilling a large amount of Softdon Link on a carpet sample made from the nylon 66 fiber of the present invention. 3785 in this test
ml (1 gallon) of 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 dye in the soft drink was 0.054 g /. The carpet sample was made in the manner described in Example 2. However, half of the sample was made from yarns with fibers treated with Intralatex N and the other half (control) was Intralatex N
Was made from the corresponding yarn with untreated fibers. 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. 40) was found to remain in one half of the carpet sample made from the inventive fibers, whereas 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 Two nylon carpet yarns were produced in this example, one according to the invention (soil barrier yarn) and one according to the state of the art (control yarn). The yarns were then similarly treated to make cut pipe 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.

60 denier (60d)
pf) nylon 66 is extruded downward through a 300-hole spinneret hole at a melt temperature of 282 ° C into a normal spinning cylinder about 1.8 m long to form a corresponding number of melt streams. did. The spinning tube was used to undergo ambient temperature cooling air cross flow at a velocity 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 single fibers are sent from the conditioner tube to a conventional metering agent application device, where they contain a stain blocker and a fluorine compound in amounts sufficient to provide 3500 ppm stain 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. The yarn was then fed around a drive supply roll (450 m / min) and its associated separator roll 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. The tow was drawn on rolls to yield nominally 18 dpf (denier per filament) tow, which was chopped in a conventional packing box and cut into 19.25 cm (7 1/2 inch) staples. The staples are carded, drafted, and spun by a conventional ring spinning machine, and about 177 times per 1 m in the Z direction (1
77tpm) [4.5 times per inch (4.5tpi)] A 31/2 count single yarn having a twist was obtained. 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. A carpet of saxony construction was made from each yarn. Each yarn was 27.6 inches per 10 cm (stitch per inch) and was tufted on a 5/32 gauge cut pile tufting machine for the primary backing. The pile height was 2.2 cm (7/8 inch) and 32 ounces of yarn per square yard of carpet were used. Each carpet was dyed a light beige color in a beck. The secondary backing was glued to the primary backing. Each carpet was subjected to the following tests.

For each carpet sample, red die before passing
Tested to determine resistance to No. 40. Example 4
An aqueous solution of the dye was prepared at a concentration of 0.054 g / as described in 1. and used for testing carpet samples. Five open cylinders with an inner diameter of 2.54 cm and a length of 10 cm 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 carpet No.4 for each carpet sample
The 0 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.

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.

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 shows the dirt barrier yarn after the first exposure to 128,000 times and the dirt test (invention).
It is a photograph of a carpet made from. Figure 6 first
3 is a photograph of a control yarn after being 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 picture was taken with the same conditions reduced to 1 / 2.67. The yarns in each carpet are those shown in FIGS. 4 and 6 in which the fibers of the yarns used to make the carpet shown in FIGS. 3 and 5 are coated according to the present invention. The yarn used to make the (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. "First" in Figs.
The word "before" means before passing, and in Figs. 5 and 6, the word "dirty" means after passing. 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 influence of a stain blocking agent and a fluorine compound on the stain resistance of nylon fibers before passage. FIG. 3 is a photograph of a carpet (fiber form) made from a dirt barrier yarn (invention) before passing and after a dirt test. FIG. 4 is a photograph of a carpet (fiber form) made from control yarns before passing and after being 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 it was first exposed to 128,000 passes and then subjected to a stain test.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 59-228071 (JP, A) JP 59-15576 (JP, A) JP 48-4800 (JP, A) JP 53- 122900 (JP, A)

Claims (9)

(57) [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 stain-resistant nylon fiber which is not dyed, 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, (Where X is hydrogen or a cation). ] And at least 40% of the above repeating units are —SO ₃ X
A group, and at least 40% of the above repeating units,
Next join, And (b) a mixed condensation product of naphthalene monosulfonic acid with dihydroxydiphenyl sulfone and formaldehyde, wherein the coating contains one or more fluorine compounds. And, when made on carpet, it retains a greater degree of resistance to initial stains after passage, compared to the case where the fluorine compound was omitted from this coating, undyed stain-resistant nylon. fiber. 2. 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. 3. 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. 4. The fiber according to claim 1, wherein the stain blocking agent is a mixed condensation product of phenolsulfonic acid, dihydroxydiphenolsulfone and formaldehyde. 5. The fiber according to claim 1, wherein the stain blocking agent is a mixed condensation product of naphthalene monosulfonic acid, dihydroxydiphenyl sulfone and formaldehyde. 6. A coating containing one or more stain-blocking agents on the surface, which has 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: [However, R is a group which may be the same or different for each unit, and is hydrogen, -SO ₃ X, (Where X is hydrogen or a cation). ] And at least 40% of the above repeating units are —SO ₃ X
A group, and at least 40% of the above repeating units,
Next join, And (b) a mixed condensation product of naphthalene monosulfonic acid with dihydroxydiphenyl sulfone and formaldehyde, wherein the coating contains one or more fluorine compounds. And made of stain-resistant nylon fiber that, when made on carpet, retains a greater degree of initial dirt resistance after passage, as compared to the case where the fluorine compound is omitted from this coating Yarn. 7. A pile essentially consisting of the following nylon fibers:
That is: It has a coating containing one or more stain blockers on its surface, the dye absorption test value at 25 ° C. is almost 0, 100 ° C.
A stain-resistant nylon fiber having a dye absorption test value of 30% or more, and the stain-blocking agent (a) essentially comprises 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, (Where X is hydrogen or a cation). ] And at least 40% of the above repeating units are —SO ₃ X
A group, and at least 40% of the above repeating units,
Next join, Is selected from the group consisting of: (b) a mixed condensation product of naphthalene monosulfonic acid, dihydroxydiphenyl sulfone, and formaldehyde, and the coating contains one or more fluorine compounds. , A carpet made of stain-resistant nylon fiber, which retains a greater degree of resistance to initial stains after passage, as compared to the case where the fluorine compound is omitted from this coating. 8. A coating having one or more stain-blocking agents on its surface, which has 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 stain-resistant nylon fiber, which comprises the step of applying a spin finish containing one or more stain-blocking agents to the nylon fiber in the melt-spinning step in which the nylon fiber is produced, And the stain blocker comprises (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, (Where X is hydrogen or a cation). ] And at least 40% of the above repeating units are —SO ₃ X
A group, and at least 40% of the above repeating units,
Next join, And (b) a mixed condensation product of naphthalene monosulfonic acid with dihydroxydiphenyl sulfone and formaldehyde, wherein the finishing agent is 1
A method for producing a stain resistant nylon fiber, which comprises one or more fluorine compounds in addition to one or more stain blocking agents. 9. The weight of nylon is 0.20 to 0.35% by weight.
9. The method of claim 8 wherein the soil barrier agent and the fluorine compound are present in an amount sufficient to provide the soil barrier agent and the fiber coated with 450 to 650 ppm fluorine.