CN1198013C - Colored bleach-resistant pile fabrics and floor mat articles comprising said pile fabrics - Google Patents

Abstract

This invention relates to new dyeing systems for nylon pile fabrics which are free from chrome-metallized dyestuffs and which comprise at least one cobalt-metallized dyestuff and at least one milling acid dyestuff. Such systems provide highly desirable and effective colorations within target pile fabrics and also provide dramatic improvements in bleach resistance to the nylon fabric surface. The inventive colored pile fabrics are utilized generally as components within launderable floor mat articles which require periodic cleaning with bleach-containing formulations. Thus, the inventive colored fabrics do not exhibit any appreciable reduction in color after such continuous, periodic rigorous cleaning procedures. Floor mats comprised of such inventive colored pile fabrics as well as the particular dyestuff compositions themselves are also encompassed within this invention. Furthermore, methods of coloring pile fabrics with dyestuffs including a heated topical overspray treatment to provide improvements in lightfastness and washfastness are also included.

Description

Dyed bleach-resistant pile fabrics and carpet articles containing such pile fabrics

field of invention

The present invention relates to a novel dye system for nylon fleece which does not contain chromium metallized dyes and which comprises at least one cobalt metallized dye and at least one milling resistant acid dye. The system advantageously provides the desired and effective dyeing of the targeted pile fabrics while also significantly improving the rinse resistance of the nylon fiber surface. The dyed pile fabrics of the present invention are typically used as components of washable carpets which require periodic cleaning with formulations containing a bleaching component. Thus, the dyed fabrics of the present invention do not exhibit significant color fading after such continuous, cyclically severe laundering. Carpets comprising the pile fabrics of the present invention are included in the present invention as well as the specific dye compositions themselves. In addition, the present invention also relates to a method for dyeing pile fabrics with dyestuffs, which includes heating partial overspray treatment to improve light fastness and washing fastness.

Background of the invention

The US patents listed below are incorporated by reference in their entirety.

Pile fabrics, especially fringed fabrics, have been used in many fields for many years. The most famous use is for carpets. A particular class of carpets are those comprising pile. Rugs have long been used to remove dust from the soles of people's shoes, especially in places like doorways that people walk through. Water, dirt and debris can easily stick to shoes, especially in harsh climates, especially in places such as grass or mud. These unwanted debris that may stain the floor need to be removed before people enter the room. As desired, such outdoor rugs naturally require frequent, repeated washing and drying cycles to remove dirt and debris that accumulates during use. Furthermore, such cleaning processes typically place the soiled pile fabric in a bleach formulation to thoroughly remove dirt and debris as well as to kill unwanted and potentially harmful microorganisms on the carpet surface. Typically, such carpet rental services often take back soiled carpets from users and provide clean ones. These dirty carpets are usually cleaned and dried in industrial cleaning machines (such as in rotary washing and drying machines), and then sent to other users to replace the newly dirty carpets.

Carpets and/or dust removal rugs have been developed in the past to provide a simple method of scraping dirt from the soles of shoes with a hard substance. Examples of such carpets or carpet piles are disclosed in U.S. Patent 1,008,618 to skowronski et al; U.S. Patent 5,227,214 of Nagahama et al., U.S. Patent 5,305,565 of Nagahama et al., U.S. Patent 5,350,478 of Bojstrup et al., U.S. Patent 5,680,826 of Nagahama et al., and French patent 1211755 of Cosyntex SA and PCT application 95/30040 of Kleen-Tex Industries, Inc., the above patents All are incorporated herein by reference. All do not mention the industrial washing method of carpet in the prior art. Other examples of carpet articles are described in US Patent 5,707,469 to Hixson et al., US Patent 5,645,914 to Horowitz and US Patent 4,741,065 to Parkins.

These fleeces can be dyed and/or printed with dyes, as desired by those of ordinary skill, to obtain aesthetically pleasing results for placement around door entrances in shopping malls, near refrigerators and freezers, and the like. Since such dyed fleece must withstand frequent harsh physical or chemical laundering, the dyes used to provide the desired dyeing described above must be able to withstand bleach as well as harsh industrial-grade spin washing and drying processes.

Metallized dyes have been used to dye such pile fabrics to achieve a certain shade or pattern in order to provide the consumer with an aesthetically pleasing carpet product that also has beneficial bleach resistance properties. Chromium metallizing dyes constitute the most important class of dyes used in this fleece dyeing process. These dyes have historically been used to provide excellent stain and bleach resistance to targeted carpet substrates. But these chromium metallization compounds have recently fallen out of favor due to safety concerns at the industrial level. In particular, dyes containing chromium(VI)-metal complexes have been banned in Europe. Moreover, all dyes containing metallic chromium have been discontinued in Japan. Although this detrimental effect is not as common as the use of dyes containing other valence states (such as chromium(III)), due to new information on the dangers of using dyes containing chromium(VI), all dyes have recently been excluded from the pile dyeing process. chromium metallization dyes. Therefore, it is generally believed that there is a need to replace this potentially dangerous, relatively safe, chromium-free metallizing dye product. So far, this problem has not been solved in the pile fabric technology, especially in carpet products. Therefore, prior art also does not provide any reference or suggestion for carpet rental, washing industry to solve this problem, to replace this good performance chromium metallization dye.

Purpose of the invention and description of the invention

Accordingly, it is an object of the present invention to provide a dyed fleece fabric which is highly resistant to bleaching. Another object of the present invention is to provide a carpet article comprising a dyed pile fabric which is dyed well without the use of chromium metallizing dyes. It is a further object of the present invention to provide a carpet product comprising the above dyed pile fabric which can withstand periodic bleach washes without exhibiting significant discoloration by treatment with the above bleach components.

Accordingly, the present invention includes a fleece fabric comprising synthetic fibers (preferably nylon, more preferably solution-dyed nylon), wherein at least a portion of said synthetic fibers are dyed with at least two dyes, the first dye being selected from at least one cobalt metallizing dye, and a second dye selected from at least one milling-resistant acid dye; wherein the synthetic fiber has not been dyed with any chromium metallizing dye. The present invention also includes a carpet article comprising the above-mentioned pile fabric. This combination of specific dyes provides excellent durable dyeing, wash fastness, weather fastness and bleach resistance to targeted fleece fabrics.

Therefore, the synthetic fibers of the fleece of the present invention may be any man-made fibers. These fibers may be selected from, but are not limited to, polyester, polyamide (nylon, such as nylon-6, preferably nylon-6,6), polypropylene, glass fibers, etc., and mixtures of these fibers. The fibers can be coarse or fine in structure. The above-mentioned individual fibers may have a denier number between about 10 and about 200, preferably about 20 to about 100, more preferably about 20 to about 25, and most preferably about 23. A bundle of such fibers may preferably be twisted together to form a yarn (preferably between about 40 and 80 twisted together in this way, most preferably about 60), and then multiple strands of such yarn (e.g. 3 strands) are further twisted Together to form the final yarn structure, which is applied to the target product pile fabric. As mentioned above, of particular interest to the present invention are 100% solution dyed nylon fibers. This pile fabric provides the best pile surface for overprinting of different dyes for optimum dyeing and shade of the carpet. The fiber structure is typically nylon-6,6, having a denier of about 10 to about 30, preferably about 20 to about 25, twisted together (eg, about 60) to form a 3-ply structure. A preferred solution-dyed nylon fiber is commercially available, by way of example only, from Camac Corporation. Such fibers have been dyed with various dyes in the past, but there is no reference or suggestion for the present invention to utilize a specific mixture of cobalt metallizing dyes and milling resistant acid dyes.

Cobalt metallized dyes have been widely used in the dyeing of various fibers, and in the past, the most important ones were used for the dyeing of polyamide. For example, US Patent 3,658,460 to Mikula, US Patent 3,221,004 to Neier, and US Patent 2,374,106 to Kvalnes et al., all discuss such dyeing processes. The term "cobalt-metallized" is intended to include any class of dyes with water-soluble groups (such as carboxyl, sulfonic acid, sulfonimide, etc.), which also include Cobalt metal ions complexed with moieties such as azo, disazo, methine dyes, diazo, and the like. Thus, by way of example only, azo compounds complexed with cobalt metal, while also containing at least one water-soluble group, are encompassed within the term cobalt metallated dye. Specific types of cobalt metallating dyes that may be used in the present invention include, but are not limited to, Isolan Bordeaux R 220 (available from DyStar), Kayakalan ^™ BrownGL (available from Nippon Kayaku), and Irgalan® Yellow 3RL 250% (available from Ciba ). It is well understood and appreciated by those of ordinary skill in the art that combinations of any of these dyes can be produced to provide different shades and shades to the target carpet. Pile fabrics dyed with this dye generally have excellent weather fastness and at the same time have excellent coloring effects (blue, red, yellow, green, gray, and other colors, available in different shades and shades). Since most carpet products (eg, including a fleece) are placed on the outside of a hallway, exposure to the outdoor environment is a major concern for such products. The above-mentioned dyes are capable of providing such desired characteristics. Milling-resistant acid dyes have been used to dye other types of fibers, such as wool (eg, US Patent 4,436,521 to Annen et al.). The term "milling acid" mainly includes dyes containing acidic groups (such as sulfonic acid, carboxylic acid, phthalic acid, etc.) and containing no metal components in any part of the dye. This term is acceptable to those of ordinary skill in the art (these dyes are very similar to the metallized dyes mentioned above, but do not contain the above metals). However, the prior art does not teach the combined use of these two dyes in the dyeing process of carpets. Such dyes have good bleach resistance properties required for the fleece fabrics of the present invention, especially for those fabrics where the dye must be subjected to severe periodic cleaning (including bleaching). Specific types of milling-resistant acid dyes that may be used in the present invention include, but are not limited to, AminylRubine FD-BL ^™ (available from Sumitomo), Supranol® Fast Blue GN 167% (available from DySta), and Supranol® Orange GSN (available from from DyStar). However, any milling-resistant acid dye can be used, and the above examples are not exhaustive.

Compositions containing the above two types of dyes can be applied to pile fabrics in various ways. Possible dyeing methods include the following examples: jet dyeing, spray dyeing, exhaust dyeing, brush dyeing, and the like. Among them, the spray dyeing method is the most preferred. In this method, a combination of multiple independent nozzles can be used to dye different patterns for the fabric, and a single target fiber can also be fully dyed. Millitron(R) and Chromojet(R) dyeing machines were used in the spray dyeing process described above.

The light fastness and washing fastness of the fleece fabric of the present invention can reach an acceptable level when the above-mentioned cobalt metallized dye and milling-resistant dye are used alone. However, both of the above properties can be improved with topical overspray, just as an example, this process can be printed on the target fleece with the desired dye composition, steamed (to improve the color of the fleece). Fastness), washed with water to remove excess dye before application. Generally, such topical overspray should include the step of coating the fleece (or, in fact, coating each individual fleece) with a polymer finishing agent (Finishing agent), which acts as Protection against environmental and atmospheric exposure and other possible damage. A specific example of a topical overspray includes SunliFe® EPS-2 produced by Emori Shoji, which contains an anionic polymeric finish. An aqueous solution (2% concentration) of the above topical overspray has a pH of approximately 2.0. This is mainly due to the relatively high amount of organic acid (eg acetic acid) contained in the above composition. In general, we have found that compositions containing various concentrations of the above topical oversprays provide beneficial finish coats (levels of protection) for different dyes, respectively. Furthermore, we have surprisingly found that heating the composition to a temperature above at least about 70°C, preferably above about 85°C, is especially important for applying the above-described topical oversprays. At such a higher temperature, the washing fastness and light fastness of the fleece fabric of the present invention not only have a corresponding improvement compared with the time of not using this overspray agent, but also compared with that of using this local overspray agent. agent, but it is only heated to room temperature or lower than 70°C and then added to the fleece fabric of the present invention, there is a corresponding improvement. There is no reference or suggestion in the prior art to use a localized overspray procedure to protect fleece fabrics from reduced color fastness due to environmental and/or atmospheric exposure factors.

Thus, the fleece fabric of the present invention has been dyed with a specific dye composition, optionally treated with a hot topical overspray. This product has the beautiful texture and shade of the cobalt metallized dyes mentioned above, but the dyeing effect is not compromised by the additional use of acid fast dyes for bleach resistance. The above findings require extensive reference to various types of metallizing dyes (except of course chromium metallizing dyes). Even with an appropriate stain, the chosen dye needs to be bleach-resistant so that it can replace the aforementioned chromium metallization dyes. We have found that anti-bleach properties cannot be achieved by adding other metallized dyes alone, additional agents are required to achieve this property. After a large number of further experiments, we found that milling-resistant dyes can improve the bleaching resistance of the above-mentioned fabrics without damaging the dyeing effect brought by cobalt metallized dyes. For the above-mentioned combined application, no reference or suitable suggestion can be obtained from the prior art.

The carpet articles described above may generally contain any amount of the dyed fleece of the present invention. Other types of fibers can also be added, such as cotton, wool, etc., as well as undyed synthetic fibers. A key component of the carpet of the present invention is at least a portion of the dyed pile fabric of the present invention. Pile fabrics of this invention, or standard, are typically tufted on a pile substrate prior to bonding it to the carpet article itself. Any standard fleece substrate, both woven and nonwoven, can be used. The pile substrate may comprise synthetic or natural fibers including, by way of example only, polyester, polyamide, cotton, sisal, wool, and the like.

Typically, the above-mentioned carpet articles may also comprise rubber bands. The carpet fiber is placed on the above-mentioned rubber belt after being tufted on the pile substrate, and then the whole composition is subjected to high vulcanization temperature and pressure (for example, the pressure is from about 172.375kPa (25pis) to about 275.8kPa (40pis), and the temperature is from about 148.89°C (300°F) to about 420.44°C (400°F) for between about 30 seconds and about 20 minutes). In this way, the substrate and the fleece adhere to the rubber belt under this vulcanization pressure. US Patent No. 585,565 to Nagahama et al., previously incorporated by reference, describes a method of making a carpet comprising a carpet pile fabric, a carpet pile substrate and a rubber belt. Nothing in this reference mentions the importance of good replacement of chromium metallizing dyes with specific metallizing dyes and milling resistant acid dyes for dyeing pile fabrics. It should be further pointed out that the dye combination used in the fleece of the present invention must be able to withstand high temperature and pressure. The cobalt metal mordant dyes and milling-resistant acid dyes applied to the target pile fabrics can meet the above selection criteria.

As stated above, the present invention in its broadest sense relates to a pile fabric dyed with a combination of cobalt metallized dyes and milling-resistant acid dyes; these pile fabrics may be applied to or contained in carpets, rugs , Cushions, Wall cladding materials, Automotive interior materials, etc. Detailed Description of Preferred Facts

The following are preferred embodiments of the present invention, and these embodiments do not limit the protection scope of the present invention.

Example 1

An undyed solution-dyed nylon fleece comprising very fine three strands (each individual fiber having a denier of about 23, each yarn comprising about 60 intertwined fibers (total denier of about 1380) , each three-ply yarn structure having a denier of about 4140) was placed in a Millitro(R)-brand jet dyeing machine. Fibers are dyed in a red pattern with black discrete dots. Colorants containing the following compositions (each in aqueous solution) are sprayed onto the fleece surface:

Table 1

Dye Concentration (g/l)

Isolan® Bordeaux R220 0.5200

Supranol® Orange GSN 2.0000

Kayakalan® Brown GL 0.7280

Water Balance

Add thickener (Kelzan S), adjust the viscosity of above-mentioned composition to be about 450cps. The above-mentioned dyed fleece exhibits an excellent full red color. The fleece is then laundered in a standard commercial rotary washer and dryer, including cleaning the fleece with a composition containing chlorine bleach. The fleece showed no significant color fading after ten repeated washes. Then, the fleece was placed on top of the rubber band and vulcanized for 15 minutes. Its color did not significantly change after the above-mentioned high-temperature and high-pressure treatment. Finally, carpets containing the above described fleece (invention) were subjected to performance testing by placing them in an outdoor entrance for a period of 4 weeks. After one more wash cycle as described above, the carpet did not show any visually significant change in shade and shade. The pile carpets of the present invention were compared to carpets made from red fleece dyed with standard chromium metallizing dyes. After bleaching and exposure to the xenon arc light aging tester device, using the gray scale (empirical method test), all the anti-bleaching fastness and weather resistance (light fastness) performance of the fabric of the present invention have all reached or exceeded those used in the present invention. To compare fabrics dyed with chromium metallizing dyes.

Example 2

Undyed undyed nylon fleece (each individual fiber having a denier number of about 23, each yarn comprising about 60 fibers twisted together (total denier number about 1380) was dyed from very fine three-ply solution , each three-ply yarn structure having a denier of about 4140) was placed in a Millitro(R)-brand jet dyeing machine. The fibers are dyed in a green pattern with black discrete dots. Spray a coloring agent containing the following composition (in the form of an aqueous solution) onto the surface of the pile fabric:

Table 2

Dye Concentration (g/l)

Isolan® Bordeaux R220 0.6540

Supranol® Fast Blue GN 2.7380

Irgalan® Yellow 3RL 0.0196

Aminyl rubine ^TM Fd-BL 0.6540

Water Balance

Add thickener (Kelzan S), adjust the viscosity of above-mentioned composition to be about 450cps. The above-mentioned dyed fleece exhibits an excellent full green color. The fleece is then laundered using a standard commercial spin wash and dryer, including the use of chlorine bleach-containing compositions for cleaning the fleece. The fleece described above showed no significant color fading after ten repeated washings. Then, the fleece was placed on top of the rubber band and vulcanized for 15 minutes. Its color did not significantly change after the above-mentioned high-temperature and high-pressure treatment. Finally, carpets containing the above described fleece (invention) were subjected to performance testing by placing them in an outdoor entrance for a period of 4 weeks. The carpet did not show any visually significant change in shade and shade after the above mentioned laundering process. The pile carpets of the present invention were compared to carpets made from red fleece dyed with standard chromium metallizing dyes. After bleaching and exposure to the xenon arc light aging tester device, using the gray scale (empirical method test), all the anti-bleaching fastness and weather resistance (light fastness) performance of the fabric of the present invention have all reached or exceeded those used in the present invention. To compare fabrics dyed with chromium metallizing dyes.

Example 3

Undyed, solution-dyed nylon fleece from very fine triple strands (with a denier of about 20-25 per individual fiber) was placed in a Millitro(R)-brand jet dyeing machine. The fabric was dyed with dyes of the same composition as in Table 1 in a red pattern with black discrete dots. Then above-mentioned fleece is steamed (water steam is heated to more than about 212 ℃), and then the excess dyestuff on the surface of the fiber is washed away. Then, the above-mentioned fleece was thoroughly sprayed with the SunliFe(R) EPS-2 composition preheated to 85°C, and then dried. The above treated fleece is laundered in a standard commercial spin washer, dryer, including the use of chlorine bleach-containing compositions for cleaning the fleece. The fleece described above showed no significant color fading after ten repeated washings. The fleece was then placed on top of the rubber band and vulcanized for 15 minutes. Its color did not significantly change after the above-mentioned high-temperature and high-pressure treatment. Finally, carpets containing the above described fleece (invention) were subjected to performance testing by placing them in an outdoor entrance for a period of 4 weeks. The carpet did not show any visually significant change in shade and shade after the above mentioned laundering process. The pile carpets of the present invention were compared to carpets made from red fleece dyed with standard chromium metallizing dyes. After bleaching and exposure to the xenon arc light aging tester device, using the gray scale (empirical method test), all the anti-bleaching fastness and weather resistance (light fastness) performance of the fabric of the present invention have all reached or exceeded those used in the present invention. To compare fabrics dyed with chromium metallizing dyes.

While certain specific features of the invention have been described above, it is to be understood that it is obvious that the invention is not limited to any particular setting or practice since modifications or other modifications will no doubt occur to those skilled in the art of the invention. A factual scheme consistent with the principles of the invention. Accordingly, it is intended by the appended claims to cover any modification of the features included within the meaning, spirit and scope of the invention.

Claims (8)

1. A fleece fabric comprising synthetic fibers, wherein at least a part/majority of said synthetic fibers are colored and exhibit bleach-resistant properties; wherein said plurality of synthetic fibers are simultaneously colored by a colorant formulation present therein, so Said colorant consists of at most two different types of dyes, the first type being at least one cobalt metallized dye and the second type being at least one milling-resistant acid dye. 2. The fleece according to claim 1, wherein the synthetic fibers in the fleece are composed of nylon fibers. 3. The fleece fabric according to claim 2, wherein the nylon fibers are solution-dyed nylon fibers. 4. A carpet comprising the pile fabric of claim 1. 5. A carpet comprising the pile fabric of claim 2. 6. A carpet comprising the pile fabric of claim 3. 7. A method for dyeing synthetic pile fibers in pile fabrics, comprising the following steps: (a) providing said synthetic pile fibers; (b) dyeing said synthetic pile fibers with a composition comprising at least one cobalt metallized dye and at least one milling-resistant acid dye; (c) optionally steaming said dyed pile fibers; (d) optionally washing excess dyestuff on the pile fibers; (e) optionally providing a topical overspray composition heated to at least 70°C; and (F) optionally applying the topical overspray composition described in step (e) to said dyed pile fibers. 8. The method of claim 7, wherein said synthetic fleece fibers consist of nylon, and wherein steps (c) to (e) are present.