MXPA99010647A - Blended dyes and process for dyeing polypropylene fibers - Google Patents

Abstract

An improved method of dyeing a polyolefin material, and preferably a polypropylene based fiber, involves a disperse dye mix including a selected plurality of disperse dyes from the same primary color group. Each dye within the mix and the concentration of each dye within the mix is selected by testing individual disperse dye solutions with an undyed sample and determining the maximum dye concentration which will produce an acceptable crocking test for that dye. A plurality of disperse dyes within the mix are each at a concentration of at least 75%of the maximum dye concentration for that individual dye. The selected dye mix is used to prepare a disperse dye mix solution which is then contacted with the polyolefin material to reliably dye the material without fastness problems. A red dye mix, a blue dye mix, and the yellow dye mix may each be prepared and may each be separately used to dye polypropylene fibers with relatively dark shade without crocking problems. Different proportions of each of the three dye mixes may be used to dye polypropylene fibers at various selected shades and color depths.

Description

MIXED DYES AND PROCESS FOR DYEING POLYPROPYLENE FIBERS DESCRIPTION OF THE INVENTION The present invention relates to compositions of dyeing mixtures and to a method for selecting dyes suitable for dyeing polyolefin materials, and particularly for dyeing polypropylene fibers. According to the method of the invention, the polypropylene fibers can be reliably dyed at atmospheric pressure and the dyed fibers exhibit good solidity. The desired dyeing can be mixed of separate compositions within the particular primary color group and each consists of a plurality of selected dyeing in selected proportions within the dyeing mixture, thereby allowing the dyeing of polypropylene fibers in various shades of water depth. color. The homopolyester fibers can be easily dyed with various types of dyes, and various dyes and dyeing compositions have been devised which are particularly suitable for dyeing polyester fibers. Exemplary patents directed to blends and dyeing compositions for dyeing polyester fibers are U.S. Patent Nos. 3,966,399, 3,989,449, 4,362,530, 4,516,979, 5,092,905, and 5,420,254. Disperse dyes can conventionally be applied to polyester fibers using either a bath process or a printing process, as described in US Patent Mo. 4,464,180. Particular problems are sometimes associated with the dyeing of polyesters with a selected yellow color tone, and the varied technology is particularly directed to this problem, as described in U.S. Patent No. 4,439,207. U.S. Patent No. 4,840,643 discloses a combination of trichromatic dyeing suitable for continuously dyeing the polyester fibers to allegedly result in excellent solidity properties. Various processes have been used to dye both polyester fibers and polyamide fibers which are commonly used in the carpet industry. U.S. Patent Nos. 3,953,168, 4,125,371, 4,199,813, 4,218,217, 4,255,154, 4,579,561, 4,801,303, 5,196,031, and 5,294,231 teach variations of techniques and processes for dyeing polyamide or polyester fibers. U.S. Patent No. 4,185,959, discloses a technique for dyeing polyester fibers in a dyeing bath containing at least nine dispersed dyes having different chemical structures. U.S. Patent Nos. 4,645,510 and 5,484,456 are directed to dyeing methods particularly designed to dye cellulose fibers.

Various techniques and dyeing have been used to improve the light fastness of dyed polyester fibers. U.S. Patent No. 4,557,730 discloses dyes and dyeing methods particularly suitable for dyeing polyester materials used in the automotive industry. U.S. Patent No. 4,351,641, is directed to a technique for continuously dyeing hair fabrics, such as carpets and fabrics for upholstery, which exhibit a uniform tone in the cross direction of the machine. Various types of stained fibers of polyester and cellulose can be subjected to a reduction of the cleaning technique after dyeing in order to remove the scattered dye molecules that have not diffused completely into the fiber. U.S. Patent No. 4,286,961 exemplifies the technology aimed at reducing the cleaning of dispersed dyes. When staining polyester fibers with disperse dyes, several dyes instead of a dye have been used to have very dark shades. Since each dye has its own saturation rate at which the dye absorption rate is slower and lower, the increase in depth decreases relative to the amount of dye available in the dyeing bath. A depth of hue that is much more Darkness can be obtained with several dyes in a shorter time than when only one dye is used. Three or four dyes in this way can be combined in a mixed dye product and applied to the polyester to result in a darker shade at lower concentration levels and at a faster dyeing rate than what one would have used if only I would have used a single dye in the dyeing process. If the desired production can not be obtained when dyeing polyester with dispersed dyeings at atmospheric temperatures, the polyester can be easily dyed under high pressures and temperatures. More than 90% of the polyester fibers and their blends with cellulose fibers are stained under pressure, 121 ° C-132.2 ° C (for example 250 ° F to 270 ° F). The deep shades of polyester are conventionally cleaned by reduction when necessary. This process involves the treatment of stained fiber in an alkaline reduction bath, during which the dye is chemically destroyed. Since the color volume is trapped deep within the fiber, an excellent peel strength can still be achieved after cleaning the stained polyester fibers by reduction. The use of polypropylene in the manufacture of carpets, has suffered a dramatic growth since the 80 's. Polyolefins, and particularly polypropylene, are hydrophobic and difficult to dye with disperse dyes since they lack dyeing sites in which the dye molecules can bind. Van der Waals forces and hydrogen bonds are often given as the reason for dyes to have affinity for polymers. Polyolefins also can not be dyed with acid dyes, since they lack basic sites with which the dye can form a salt bond. Those experienced in the polypropylene fiber manufacturing technique have long recognized that the inability to successfully dye polypropylene has limited their growth, particularly to uses where color design and flexibility is required. Therefore, much of the polypropylene currently used in the carpet industry is dyed with pigments during the extrusion process. In the early 90's, the Lyondell Petrochemical Company developed an improved polypropylene resin which was successfully used to manufacture fibers suitable for the carpet industry. The new polypropylene fibers could be dyed by dispersion under atmospheric pressure and conventional dyeing temperature conditions. This dyeable polypropylene composition is described in U.S. Patent Nos. 5,468,259, 5,550,192 and 5,576,366, which have been introduced by Lyondell under the name of KROMALON ™. While polypropylene fibers developed with this technology exhibit incredible promise, the fibers and materials made by this new polypropylene composition have experienced problems with dyeability and strength. Numerous disperse dyes that are commonly used to successfully dye polyester, polyamide and acetate materials have not performed well when stained with KROMALON. Some of these dyes do not compose well to form darker tones and others have insufficient solidity properties. Polyester and polyamide fibers can be easily dyed with dispersed dyes since there is a mechanical bond of the dye with the expanded fiber. In polypropylene, this mechanical bond does not occur since polypropylene does not absorb well or swell in water. The level of saturation of dyeing when dyeing the polypropylene in this way is very low compared to the level of saturation of dyeing when dyeing polyester, and the dyed polypropylene generally exhibits a fastness of detachment and fastness to very poor treatment compared to the polyester dyed. In general, the saturation curve for KROMALON is thus very markedly different than the saturation curve for polyesters and polyamides. Since the saturation concentration of many tints is quite low when KROMALON is dyed compared to the saturation concentration for the same polyester dyes, attempts to dye KROMALON to obtain a very dark shade often result in 50% or more of the dye not exhausted in the material KROMALON, which results in dyed fibers which have a fastness to loosening and rubbing very poor. While polyesters can be conventionally dyed to very dark depths with scattered dyeings, extreme difficulties are encountered when trying to reach the same depths in dark tones with adequate strength when the KROMALON is dyed. As mentioned earlier, the polyester fibers, which are stained by dispersion, can be easily cleaned by reduction to remove the dye-free particles. Polyester reduction cleaning typically occurs at 71.1 ° C to 82.2 ° C (160 ° F to 180 ° F) using a mixture of caustic soda and sodium hydrosulfite. If this same cleaning by reduction is performed on the polypropylene, it will adversely alter the tone to a significant degree. The reduction strength of the polyester treatment occurs only in the outer layer of the fiber. Polypropylene is not as dense as polyester, and is therefore more porous in that it serves to reduce the reduction treatment into the fiber, thereby destroying the color.

Therefore, KROMALON has a dye fixation mechanism which is markedly different from the dye fixation mechanism used to dye both polyesters and polyamides. High-temperature dyeing of KROMALON does not appear to result in a significant improvement in color production which is experienced when polyester is dyed at high temperatures. The dyeing of polyesters is often improved with the use of carriers. Typical carriers are organic compounds, such as butyl benzoate, biphenyl, trichlorobenzene, which can be emulsified in water and thus allow a faster dyeing. The carriers penetrate the fiber, very often by swelling the fiber and aiding the passage of the dispersed dye through the interface of the dye dispersion fiber and into the fiber. Carriers commonly used with disperse dyes for polyester dyeing are not effective to a significant degree in KROMALON fibers and those that help have other limitations such as a drastic drop in glossiness or due to their strong offensive odors. They can use for many applications. The disadvantages of the prior art are solved by the present invention. An improved process is described below to select dyes and to combine dispersed dyes, which are capable of reliably dyeing polyolefins, and particularly polypropylene. The improved method for dyeing KROMALON according to this invention, allows the dyeing operator to obtain the desired shade and darkness of the dyed substrate without the dyed fibers thereafter exhibiting peeling problems. In accordance with the present invention, different dispersed dyes are selected and placed in combination with other dispersed dyes as a function of their maximum concentration before exhibiting detachment problems. Numerous red scattered dyes can thus be combined to form a red dye composition, numerous blue dyes can be combined to form a blue dye composition, and numerous yellow dyes can be combined to form a yellow dye composition. Each dye is used at a concentration lower than its maximum concentration level which can result in a detachment. The combined dyes desirably "stack" or accumulate to result in a dark tone, but also do not "stack" to result in a dye combination which exhibits release. Each dye is generally selected in the linear area of a K / S v. Dye concentration curve, which provides conformation data obtained by the peel test.

According to the present invention, the peel tests in individual dyes in this way are used to determine the maximum concentration at which the dye can be used before resulting in a peeling problem when KROMALON is dyed. Once this concentration of maximum tincture is obtained, the dye can use a concentration and can be stacked or combined with other dyes and result in peeling problems. Each of the dyes selected within the dyeing composition in this way acts substantially independently of other dyes, thereby allowing the dye to accumulate without creating peeling problems. A dark dye color can thus be obtained by accumulating several dyes. KROMALON fibers can be reliably dyed at atmospheric pressure, thereby avoiding the high cost of pressurized dyeing equipment. The present invention provides a technique for economically dyeing polypropylene by allowing various shades and colors to be dyed without exhibiting strength problems. A maximum dye concentration for each dye is determined as a function of the detachment tests. Very dark tones of polypropylene can be dyed with good solidity using a dye mixture consisting of several dyes each within the same group of primary color, for example, red, blue or yellow. Instead of simply using a yellow, a red, and a blue dye to obtain a desired shade, the invention uses a combination of yellow dyes to result in a mixture of yellow dye, a combination of red dyes to result in mixtures of red tincture, and a combination of blue dyes to result in a mixture of blue dye. Several different dyes can be used to make each dye mixture, and each dyeing mixture can then also be used to dye a relatively dark dark tone. Four or more different dyes can thus be used from the same primary color group to obtain a specific color formulation. Each dye within the dyeing mixture is used at a concentration level at which that dye accumulates to a high degree of exhaustion, and more importantly without giving rise to a detachment problem. The very dark dyeing of KROMALON in this way is possible with a good solidity. The individual dyes forming the dyeing mixture are selected as a function of their individual performance when used alone when staining a non-dyed KROMALON sample. In general, each dye is selected at its maximum concentration which will result in a 4-5 value of peel strength, which is considered as an acceptable peel strength. When they are combined, each tincture exhausted at its own speed, substantially unoccupied by the other dyes. One can have dark tones of polypropylene dyed at atmospheric pressures and without detachment problems. For optimal results, specific dyes are selected, which have good accumulation and high K / S values. The dyes selected ideally have a good solidity of brilliance, good solidity at high humidity of ozone and oxides of nitrogen and good fastness of detachment with a minimum rating of 4-5 in depths of darkness. The dyes selected in the specific color dyeing mixture may be complementary in that one dye has good brightness strength, but a mediocre accumulation, while another dye accumulates well, but lacks acceptable brightness when used by Yes, alone. A combination of both dyes, however, can result in a final product having significantly better dyeing characteristics than each of the individual dyes. The mixed dyes forming the dyeing mixture have excellent accumulation properties with acceptable solidity in dark shades, and also sufficient brightness at less dark depths.

A blue dye composition, a red dye composition, and a yellow dye composition can thus be generated according to the process of the invention. These three types of compositions or mixtures can then be used at different percentages of blends in the dyeing process to obtain the desired color and shade. It is an object of the present invention to provide an improved method for dyeing a polyolefin which results in a desired dark shade without the dyed polyolefin exhibiting a significant peeling problem. It is another object of the present invention to improve the process for commercially dyeing polyolefins by providing various dyeing compositions each in a primary color group (e.g., red, yellow and blue) with each of two or more dye concentrations within the group. composition being determined as a function of its detachment characteristics independent of the other dyes within the same composition. Still another object of the invention is to significantly improve the commercial success of dyed polyolefins by providing a process for reliably dyeing the polyolefins at atmospheric pressure. A significant feature of the present invention is that the polypropylene fibers can be reliably dyed and used to manufacture carpets with fibers that exhibit good fastness properties. It is a further feature of the invention that an improved process for dyeing polypropylene with selected dispersed dyes is provided, resulting in an economically dyed polypropylene material. Yet another feature of the present invention is that the polypropylene fibers can be reliably dyed in various desired shades using commercially available disperse dyes. An advantage of the present invention is that the marketability of polypropylene fibers is significantly improved. Another advantage of this invention is that the polypropylene fibers can be dyed reliably either before or after the fiber becomes yarn. The use of a reasonable amount of fiber finish or fiber fiber lubricant, which is desirable for many applications, does not prevent reliable dyeing of dark colors. Another significant advantage of the invention is that only a few different primary color blends can be provided to a dyeing operator which can then reliably dye the polyolefin in eight light or dark colors and in several different shades using different shades of blends in set amounts in a color table. These and other objects, features and advantages of the present invention will be obvious from the following detailed description, wherein reference is made to the figures in the accompanying drawings. BRIEF DESCRIPTION D? THE DRAWINGS Figure 1 graphically illustrates the K / S values as a function of the dye concentration for four different yellow scattered tinctures. Figure 2 graphically represents the K / S values as a function of the dye concentration for three different red scattered tinctures. Figure 3 represents the K / S values as a function of the dye concentration for a specific dispersed dye, and also graphically represents the values of dry release after dyeing and normal dry by air and also the values of dry release for fibers lubricated after drying for 48 hours at an elevated temperature of 48.8 ° C (120 ° F). Figure 4 represents the same information as Figure 3 for another scattered dye. According to the present invention, a combination of red dye, a combination of blue dye, and a combination of yellow dye, each is made, with each dye combination including a plurality, and preferably at least four or more dyes Selected of each group of primary colors. The individual dyes which are included within the combination are selected by a dye selection process. The dispersed dye candidates that can be included in a combination can be selected initially by screening a rapid dyeing with a 0.1% concentration of a KROMALON sample material. The dyeing rinse can then be depleted in wool or polyester. If the rinse water is deeper than the stained sample, then the tincture can be considered non-economic. For the dye candidates which provided at least 80-100% yield at a concentration of 0.1%, additional dyes of polypropylene samples were made at higher concentration levels, for example, 0.25, 0.50 and 1.00%. For the KROMALON samples to which no fiber lubricant was applied, a dry release test was made after conventionally air drying the fibers. For polypropylene samples that had 0.5% lubricant applied to them, the samples were dried in an oven for 48 hours at 48.8 ° C (120 ° F). At the end of 48 hours, the dry detachment test of those samples was then performed. The maximum concentration for each dye (depends on whether the fibers had a lubricant or not) was established at a point where the detachment went from a value of 4.5 to a value of 4. Three acceptable "orkhorse" dyes were obtained: dispersed red 60 , scattered yellow 64, and disperse blue 148. (It should be understood that all dyes listed generally by color and number refer to the name in the Color index). The Gray Scale Grading System was used to test detachment in the samples, in which the solidity characteristics were evaluated in a range of 1 to 5, with 5 indicating no change, 4 being a light change indicator, 3 indicator of a notable change, 2 indicator of a significant change, and 1 being indicator of a severe change. Grades such as 3_-4 obviously could not be characterized as just a slight change, but were better than those characterized with a noticeable change. In general, ratings of 4-5 or 4 for the majority of the fibers is acceptable, and a rating of 3-4 for some fibers is of acceptable limit. Tests were conducted with numerous dispersed tinctures to determine the maximum concentration of each individual tincture before peeling, ie, before the peel value changes from 4-5 to 4. When the tincture mixtures of up to 12 different tinctures with each dyeing below its maximum concentrations before the release of the same color group were then mixed, the tests confirmed that when mixed, each dye had a performance independent of the other dyes and resulted in good color buildup and detachment. Figures 1 and 2 represent the concentration values K / S v. for different scattered tinctures. The four dyeing curves provided in Figure 1 are each for a dyeing of the yellow primary color group, and the three dyeing curves in Figure 2 are each for a dyeing of the red primary color group. The concentration curves K / S v. for specific dispersed dyes when staining unstained polypropylene samples provide useful information regarding the maximum possible dye concentration which can be used for a specific dispersed dye, which will result in an acceptable peel test, but not It can be used as a substitute for the current detachment test. In general, however, the maximum acceptable dye concentration values which will result in acceptable peel tests will be comfortably within the linear portion of the curve, as will be discussed below.

Figures 3 and 4 further illustrate the concept of the present invention, and specifically the K / S values of the dye in coordinates as a function of the dye concentration. The curves do not teach where the maximum dye concentration is that will result in an acceptable peel test. Only, to the driver the tests and currently review the values of detachment, can determine the maximum concentrations before the detachment for a specific dyeing. However, the K / S value curves for the specific dyes, if they help to predict the probable dye candidates and the estimated maximum concentration values. Specific release tests were necessary to determine the maximum concentration at which each dye could be used in the specific mixture without this dye creating a detachment problem. Referring specifically to Figure 3, the maximum concentration for the specific dyeing for the fibers began to exhibit some detachment (4-5 release value) is about 0.3%, while the same dyeing could only be used at a concentration of less of approximately 0.2% to result in an acceptable release value of 4 if a lubricant was applied to the dye. Therefore, a safe limit for this dye at a concentration of approximately 0.5% can be determined based on these tests, without taking into account whether the polypropylene material had a lubricant or not. In general, a concentration closer to 0.2% could be used successfully for this dye if little lubricant was used in the polypropylene, or if the lubricant that was used had a minimal effect on the release. Obviously, a dye concentration of approximately 0.25% can be used to dye polypropylene with this dye and not exhibit detachment but no lubricant was used. It should be understood that all dye concentration values as used herein are the percentage of dyeing for the weight of the dyed material, which is a standard expression of the dye concentration. Figure 4 provides similar data for another dye. If no lubricant was used in the sample, the dye concentration can be increased to approximately 0.3%, while an acceptable release value of 4 can still be obtained. If the lubricant was used, however, the same release value Acceptable of 4, it can only be maintained up to a dye concentration of approximately 0.1". Therefore, the data in Figure 4 show that, for this dye, the maximum concentration at which this dye can be combined in a mixture would be of 0.1% if the dyeing mixture was used to dye polypropylene which had a lubricant.A higher concentration can be used if the same mixture was used to dye polypropylene without lubricant.In many cases, a universal dyeing mixture is desired for dye several types of polypropylene with several or no lubricants in the fibers.Therefore, the concentration of 0.1% for this dye can be used in t to the universal dyeing mixture. As indicated above, each dispersed dye has its own specific strength characteristics when applied to polypropylene. The following table provides specific information for five dyes, including the percentage of dye concentration at which the detachment is equal to 4, brightness fastness characteristics, high ozone / NOx moisture characteristics, and preferred concentration. The tests of high humidity of ozone and high humidity of NOx represent tests of two cycles.

Dye A is a disperse blue 148. This dye is a tremendous accumulator, although the fastness to detachment becomes unacceptable around l 'k of concentration. All other aspects of mushroom tincture are acceptable, except at very clear depths. Tincture B is a blue Terasil HLB and is a very good dye in general, except for the accumulation. Although it was not as powerful as the dye A is better than the Dye C. The Dye C is a blue dispersed 87, which has an excellent light fastness, but is limited in its accumulation characteristics. It stops the accumulation at approximately 0.75% and from 0.5 to 0.75% there is only a very limited increase in depth. Dye D is a sparse blue 118. This dye has limited accumulation characteristics and a good light fastness when used alone. Tincture E is a disperse blue of 191, and it is an outstanding dye with good solidity to air pollution, but poor light fastness. By using moderate amounts together with the dyes A, B, C, the dyeing mixture results in an acceptable light fastness. For D Dye there is a risk when too much is used in the mixture in such a way that the resulting combination exhibits poor light fastness and also deficient ozone / NOx values.

The information provided in Table I indicates that the five dyes can be used to form the dye mixture for a specific blue dye color mixture. Of the dyes that were included in this mixture, both A and B dyeing are selected at a concentration of less than 75% of the maximum concentration which will result in an acceptable release value of. The dye C is selected from a concentration for the mixture which is only slightly less than 70% of the maximum concentration which will result in a release value of 4. Thus, at least two or more of the dyes of this mixture of five blue dyes is selected to substantially its maximum dye concentration determined for each of these two dyes. The other important point with respect to the data provided in Table I is that the preferred concentration of at least two of the dyes for the dyeing mixture was selected to have approximately the same amount at a maximum concentration for that dyeing. In other words, the preferred concentration for dyeing A is obviously 75% of its maximum concentration which will result in a release value greater than 4, while the concentration selected for dyeing B is 80% of its maximum concentration. which will result in a release value of 4. As will be seen later, the preferred concentration for the C dye is approximately 70% of its maximum dyeing concentration which will result in a release value of 4. While the The proportion of the preferred concentration for the maximum dye concentration is less for both dyes D and E, it can be seen from the above, that within an acceptable range of 10%, three of the five dyes have approximately a proportion of a preferred concentration in the mixture of dyes in the preparation with the maximum concentration of each dye which will result in an acrylic release value eptable. The above explanation is particularly important in view of graphs 3 and 4, and the desire to form an acceptable dye mixture according to the present invention while minimizing the risk of any significant detachment problem. It can be seen that the five dyes, which comprise the blue dye mixture as shown in Table I, have a combined concentration of 3.25%, which of course is significantly greater than the concentration that any of these three dyes could apply to fiber without resulting in a significant detachment problem. Since the dyes in the dyeing mixture accumulate well, in terms of their fastness properties, but do not accumulate to result in a release problem, the mixture in Table I is thus suitable for dyeing polypropylene according to with the present invention. In another example, a red mixture contains the following red dyes each in the percentage concentration listed in the following table.

Tincture A is red 146, which results in a bright pink color and accumulates well in violet. Dye B is red 60, which is satisfactory up to a concentration of 0.25%, but does not accumulate well beyond this concentration and results in poor detachment if this level of concentration increases. Tincture C is red 127, which is a weak tincture, and is less than half as strong as red 60. Tincture D is red 338, which produces a reddish orange color and accumulates extremely well. However, this tincture begins to be released at concentrations above 0.50%. The tincture E is red 50 which produces an orange hue. The tincture stops accumulating at a concentration of approximately 0.55%, and detachment is also a problem beyond this concentration. The tincture F is red 13. This is an excellent tincture in terms of accumulation, however, this tincture has a poor light fastness on its own. When used in combination with red 60 and below 0.25%, good light fastness is obtained. The tincture G is red 65 which has a good light fastness, but which should not be used at concentrations higher than 0.125%, due to the tendency to release at higher concentrations. For each of the red and blue combinations described above, the concentrations of dyes in the aggregate were from 3.3 to 4.0% and resulted in very dark shades of polypropylene being dyed with a generally good solidity. The sum of the dyeing concentrations for the individual dyes comprising a dye mixture according to the invention will typically be above 2.5, and usually in the range of 3.0% to 4.5% .. In each case, the sum of the Dye concentrations for the individual dyes in the dyeing mixture will be substantially greater than the maximum dye concentration determined for each of the individual dyeings within the dyeing mixture. The following list good dyeing candidates for a combination of yellow, red, and blue dye mixtures.

TABLE III Blue Scattered 60 (Blue Terasil BGE 200%) • Scattered Blue 291 (Azu 1 Intrasil MGS) Scattered Blue 118 (Azu 1 Terasil GBT) Blue Terasil HLB Blue Scattered 87 (Blue Intrasil FGB) Scattered Blue 148 (Navy Palanil 3RT) Scattered Blue 56 (Blue Intrasil FBL) Scattered Blue 332 (Turquoise Bafixan 2BL liq.) Primary Yellow Color, Including Orange, Ca.fe Yellow Scattered Yellow 64 (Yellow Disperite 3G 200%) Scattered Yellow 23 (Yellow Incrasil 5R) Yellow Palanil HM Scattered Coffee 19 (Yellow Dispersol D-7G) Scattered Orange 30 (Yellow Coffee Foron S-2RFL) Orange Scattered 41 (Orange) Intrasil RL) Scattered Orange 37 (Dark orange In trasil 3GH) Scattered Amaryllis 3 Scattered Orange 30 Scattered Amaryllis 42 Scattered Orange 89 Scattered Amaryllis 235 Scattered Orange 3 Scattered Amaryllis 54 Scattered Amaranth 233 (Yellow Foron S-6GL) Some selected tints are obviously They accumulated better than others. Other dyes have a generally good solidity and a minimum light rating of either 4 or? after 40 Xenon SFU, and a good detachment strength rating of 4-5, and a rating of two cycles of high humidity of ozone and high humidity of nitrogen oxides. By selecting the appropriate dyes to optimize the positive aspects of each dye, a dye can be selected so that it accumulates well or another dye that has good light fastness. In the same way, one can combine a dye with a very good solidity to ozone and NOx with a dye that does not have this same desired property. As an example, blue 87 and blue Terasil HLB have very good light fastness, but blue 87 does not accumulate well. The blue HLB accumulates better, but not as well as the blue 'dispersed 148. This blue has a very good light fastness at concentration levels as low as 0.05%. A combination of these three dyes results in a mixture with a general accumulation and excellent fastness properties. One can now add blue 291 to this mixture, which is a very good accumulator, but which has a mediocre light fastness. A moderate small amount of blue 291 gives an additional boost to the accumulation properties of this four dye mixture, while still maintaining adequate light fastness. This process can be expanded with the other additional blue dyes. Each component contributes to achieve an adequate accumulation with an acceptable solidity. Table IV represents the standard depths for the dyes evaluated by dyeing by exhaustion in KROMALON. The standard depth information provided in a format is well recognized by those skilled in the art. Basically, it should be understood that a standard depth of 1/1 is half the standard depth of 2/1. The standard depth of 110 is thus one-tenth of the standard depth of 1/1. The information provided in Table IV provides, for specific dispersed dyes, the standard depth that can be obtained at different concentrations of dyeing, and in many cases the release value for that dye at the stated concentration. The information provided in Table IV, as well as together with the concentration values K / S v. discussed above, provides very useful information for estimating which disperse dyes and maximum concentration for each disperse dye can be used to dye polypropylene without exhibiting detachment problems. The data in Table IV in this way are useful for selecting the disperse dyes for a dyeing mixture and for estimating the maximum scattered dye concentration which will result in an acceptable release for that individual dye, but again it is not a substitute for a current detachment test. TABLE IV Standard depths for the dyes evaluated by the exhaustion dye in KROMALON 100%. THE UPPER NUMBER OF THE 15"CONCENTRATION OF DYE, THE LOWER NUMBER IS THE VALUE OF PROOF OF DETACHMENT FFOFÜHDIDRD EStRN-KP. 1/50 1/25 1/20 1/12 1/10 1/6 1/5 1/3 l / 'i i / t 2/1 3.S /.

Color Red Primary Incli lyenc 0 Scarlet, Bordeaux and Violet R030 338 ol 0.25 0.5 1. 0 (5) (4-5) (3-4) (2 (Red Intrasil 4BY)) Red 50 0.1 0.25 0.5 / 1.0 (5) (4-5) (4) / (3-4) (Scarlet Intrasil 2GH) Red 127 0.1 0.25 0.5 1.0 (Red Intrasil BN- (5) (4-5) (4-5) (4) SE) Red 60 0.1 0.25 0.5 1.0 (5) (4-5) (3) (2) Ro] o Intrasil 2B 200%) Red 146 0.1 0.25 0.5 1.0 (Red Intrasil BSE) (5) (5) (4-5) (4 -5) Red 65 0.1 0.25 0.5 (4-5) (3-4) (3) (Red I trasil MG) Red 302 0.1 0.25 (Pink Terasil 3G) R030 191 0.1 / 0.25 (5) / (5) (Pink Intrasil SRL) Red 86 0.1 / 0.25 (5) / (5) (Rosa Terasil 2GIA) R030 167 0.1 0.25 / 0.50 (5) (4-5) / (3-4) (Rubine Foron S-2GFL) R030 13 0.1 0.25 0.50 1.0 (5) (4-5) (4) (3) (Bordeaux Intarsperse BA) Mixture of Reds 0.1 0.50 1.0 2.0 2.25.97 (5) (5) (5) (4-5 / 5) TABLE IV (CONTINUED) THE UPPER NUMBER OF 15"CONCENTRATION OF DYE, THE LOWER NUMBER IS THE VALUE OF PROOF OF DEPRESSING MINIMUM DEPTH STANDARD 1/50 1/25 1/20 1/12 1/10 i / or 1/5 1/3 2/2 1/1 2/1 5.5 / i Color- Blue Primary Blue 118 0.1 0.5 1.0 (Anuí Terasil GBT) Blue 60 0.1 0.5 μs Terasil BGE l'OO) Blue 291 0.1 0.5 1.0 Blue Intrasil MOS) Blue 55 0.1 redder redder Blue Intrasil FB) 0.5 1.0 Blue 54 0.1 0.5 1.0? Zul Intrasil 4F.L) Blue 148 0.1 0.5 1.0 2 ..? (Blue Intra &il Palanil 3RT) Blue 87 0.1 0.5 / 1.0 (Blue Intrasil FGB) Blue Terasil HLB 0.1 0.5 1.0 Mixture of Blues 0.1 (5) 0.5 1.0 2.0 32497 (5) (3) (4-5) Primary Yellow Color, Including Orange, Coffee a illo Yellow 23 'Yellow Intra.sil n. 0.50 i.o J.5 / 1 5P? (2.0) Orange 37 (Orange Intrasil "-, 00.5 / Di; 3GH) 1.0 Coffee 19 (Coffee Dispesol C-3G) Q, 0.5 1.0 Amrillo 64 '. Yellow Palanil 3G 200.) Mix of Yellows 0.1 0.5 1.0 2.0 ( 5) (5) (5) (4-5) More specifically, the information provided in Table IV dramatically demonstrates the increase in the color depth of the specific dyes (the mixture of reds 2.25.97, the mixture of blue 32497 and the mixture of yellows), and the resulting release results against the individual coloring matters. The data for the red primary color dyes showed that the deepest red was achieved from individual dyes in about 1/3 of depth with many dyeings peeling at depths as low as 1/25. The mixture of reds 2.25.97 shows excellent detachment results even at a depth of 2.5 / 1, two and a half times deeper than any individual component of coloring matter. It is also possible according to the present invention to select individual dyes for the dyeing mixture according to the current accumulation tests. Accordingly, unstained polypropylene samples can first be dyed with a solution having a selected dispersed dye A, then the respective samples each dyed with dye A can be attached with a plurality of solutions each containing dye B, dye C , and dye D scattered respectively, with each of the dyes B, C and D, being of the same group of primary color as the dye A. All the other information of solidity is equal, the dye B, C, and D which they accumulate better with the selected A dye then it will be selected to be combined with the A dye in the dispersed dye mixture. The material suitable for dyeing in accordance with the present invention is a polyolefin with a polypropylene base described in U.S. Patent Nos. 5,468,259 and 5,550,192, each incorporated herein by reference. This polypropylene composition to which it may be referred to as modified polypropylene, includes a selected amount of an ethylene copolymer, and preferably a copolymer of methylethylene acrylate. This material may be dyed in dispersion according to the present invention in a cost-effective manner to result in a dyed fiber which has a good light fastness., good washing fastness, and good release or de-inking properties. Although the exact theory to obtain the results of the improved dyeing is not known, one possible explanation is that there are three phases of absorption as the dye accumulates in the KROMALON: 1. part of the dye is absorbed deep within the fiber and find a place to look; 2. part of the dye enters the fiber and produces an improvement of color production, but it is not fixed enough to withstand the decolorizing action of the surfactants, oil, time and temperature; and 3. part of the tincture has nowhere to go, it is washed in the dyeing bath, and if it is not rinsed well it will create a problem of detachment at the time of dyeing. It is believed that one of the primary reasons that a dye mixture containing a plurality of dyes to disperse each within the same primary color group accumulates well to allow the polypropylene to be dyed in very dark shades without peeling problems is that Each of the selected dyes performs different functions when fixed to the polypropylene fibers. In other words, the dye A * can be fixed to the fiber either in a mechanical and / or chemical manner which is markedly different from the way in which the other dyes within the dyeing mixture are fixed to the fiber. Therefore, each of the dyes in the dyeing mixture, taking into account that it is used at a concentration lower than its maximum concentration which will result in a detachment problem for that individual dye, then it can be combined in a mixture of dyeing so that the dyes are stacked and result in the desired dark tone, but that the release concentrations of the individual dyes do not effectively pile up.

The KROMALON can thus be dyed by dispersion in long baths or can be continuously dyed by a pad-vapor or vapor-printing method. The KROMALON can also be dyed with steamers, which are commonly used in space dyeing. The steam can also be injected through non-steam in a water tank which contains the dye bath, which results in a constant boiling bath and thus the generation of steam. The ideal vapor conditions are 100% relative to humidity and temperatures of 98.8-100 ° C (210-212 ° F). The good exhaustion of the dispersed tincture can be obtained in some steamers in 3 or 4 minutes for light to medium depths and in 5 to 6 minutes for depths mediated in the dark. A steam steamer is obtained using superheated steam, and this type of steamer has been found to provide good fixing conditions for the dispersion dyeing of the KROMALON. Shorter steam times are possible when using pressurized saturated steam or above 100 ° C (212 ° F). The KROMALON can also be dyed using an unwoven fabric space impression when the base tone is first placed on the material after multi-color printing. When dyeing the KROMALON in the form of yarn it is preferable in most cases to apply a fiber lubricant to the dyed fibers to reduce the friction of fiber against fiber during the weaving and quilting steps. As explained above, this lubricant typically needs to be considered when dyeing, since the presence of a lubricant in the fibers increases the friendliness of a release problem if the specific dye concentrations in the mixture are not carefully controlled. Since the KRQMALON melts at a much lower temperature than the polyamide fibers, the KROMALON can be dried after being dyed at temperatures of less than 110 ° C (230 ° F). The polyolefin material can be successfully dyed both by exhaustion and by continuous dyeing methods. The polypropylene fibers can be dyed by dispersion according to this invention in a bath with a pH of 2.5 to 10.0, preferably 4-6. The dye is normally dispersed in water at 43.5-48.8 ° C (110-120 ° F). Physical factors, such as temperature and agitation, and auxiliary chemicals can be added to the dyebath to alter the proportion of dyeing. The agitation of the dyeing bath accelerates diffusion of dyeing in the fibers in the dyeing bath. The continuous dyeing can be carried out by any number of currently available methods. These include solid shades on the Fluiclye and Instacolor machines, and Multicolor processing involving various forms of screen printing and roller printing, rubber layers, and dye flood applicators. Jet printing, spray dyeing, and a variety of multicolored continuous processes are also allowed to be used. Different dyeing solutions can also be sprayed on the fabric or carpet made of a KROMALON composition. A small amount of defoamer can be used when dyeing by printing and padding solutions are used. If any reductive treatment is used on the dyed KROMALON, it should be much lighter than when using polyester, with a lower concentration of sodium carbonate, and performed at lower temperatures and for a shorter period of time. The KROMALON also exhibits thermal migration, which is the time / temperature migration of the saturated dye to the surface. This migration is accelerated by temperature and is further accelerated by most lubricants, oils and surfactants which are commonly applied to the yarns to allow them to process well. Mixtures and dyeing techniques for selecting dyes can be used in polyolefin materials other than polypropylene. Specifically, the techniques of the present invention can also be applied to the dyeing of polyester fibers of the poly (trimethylene terephthalate) variety as described in a document entitled "Dyeing and Staining of Poly (trimethylene terephthalate) Carpets". The following solid state test methods certified by the AATCC were used to generate the ratings (1 to 5), discussed above: AATCC light fastness test method 16-1993; AATCC test method fastness to detachment 8-1996; AATCC test method of color fastness to nitrogen oxides «n the atmosphere under high humidity 164-1992; and AATCC test method color fastness to ozone in the atmosphere under high humidity 129-1996. Various modifications to the dyed fiber compositions and to the techniques described herein for dyeing fibers may be obvious from the above description of the preferred embodiments. Although the invention has been described in detail for these embodiments, it should be understood that this explanation is for illustration and that the invention is not limited to these embodiments. The alternative dyeing compositions and techniques in this manner will be obvious to those skilled in the art in view of this disclosure, and such alternative compositions and techniques are made without departing without the spirit of the invention, which is defined by the claims.

Claims (24)

1. RI IVIHDICATION 1. A method for dyeing a polyolefin material, characterized in that it comprises: preparing various dispersed dyeing solutions, each comprising a single disperse dye at a known dye concentration; contact a sample of undyed polyolefin with each of the dispersed dye solutions, test each sample of polyolefin dyed to determine its release characteristics, for each of the various dispersed dyes, determine the concentration of maximum dyeing that will produce an acceptable peel test for each of the various dispersed tinctures within a common primary color group, selecting a plurality of dispersed tinctures each substantially at its determined maximum tincture concentration, combining the selected plurality of dispersed tinctures to form a first primary color dye mixture, prepare a dispersed dye mixture solution of the primary color dye mixture, and contact the non-dyed polyolefin material with the dispersed dye mixture solution to dye the polyolefin material.
2. 2. The method in accordance with the claim 1, characterized in that it further comprises: testing each stained polyolefin sample to determine other solidity characteristics and several of the dispersed tinctures within a common primary color group, selecting additional disperse stains each at a concentration below its tincture concentration maximum determined and depending on its other determined solidity characteristics.
3. 3. The method of compliance with the claim 2, characterized in that it additionally comprises: selecting from the various dispersed dyes within a common primary color group, additional scattered dyes each depending on their other solidity characteristics and the solidity characteristics of the other selected disperse dyes.
4. 4. The method of compliance with the claim 1, characterized in that each of the plurality of selected scattered dyes is combined with another dispersed dye at a concentration of at least 75 ?; of its determined maximum tincture concentration.
5. 5. The method of compliance with the claim 1, characterized in that each of the plurality of scattered dyes is combined with other dispersed dyes selected at a concentration which, when expressed, has a percentage of its maximum dye concentration, which is within 10% of the percentage of the other plurality of dispersed tinctures with their concentration of respective maximum tincture.
6. 6. The method of compliance with the claim 1, characterized in that it further comprises: for each several disperse dyes within a primary color group, represent K / S as a function of the dye concentration for specific dyes to help select the plurality of disperse dyes.
7. The method according to claim 1, characterized in that it also comprises: for each of the various scattered dyes within a group of primary color, represent the standard depth as a function of the dye concentration for specific dyes to help select the plurality of scattered tinctures. .
8. 8. The method according to claim 1, characterized in that the polyolefin material is a polypropylene material.
9. The method according to claim 1, characterized in that the polyolefin material is dyed with a dye mixture solution at atmospheric pressure.
10. The method according to claim 1, characterized in that it further comprises: contacting a sample of non-dyed polyolefin with a first dispersed dye solution obtained from a first selected dispersed dye; and after contacting the polyolefin sample with the first dispersed dye solution, contacting the stained sample with another prepared solution of a second dispersed dye within the same primary color group or; that the first tincture to test the accumulation ratio of the first tincture and the second tincture; and selecting first and second dyes for the dyeing mixture based on the accumulation ratio test.
11. The method according to claim 1, characterized in that the selected plurality of dispersed dyes are each of the primary yellow group and are selected from a group consisting of disperse yellow 64, dispersed yellow 23, yellow Palanil HM, coffee dispersed 19, scattered orange 30, scattered orange 41, scattered orange 37, scattered yellow 3, scattered orange 30, scattered yellow 42, scattered orange 89, scattered yellow 235, scattered orange 3, scattered yellow 54, yellow Foron S-6GL and yellow dispersed 233.
12. The method according to claim 1, characterized in that the dispersed dyes each are of the group of primary red color and are selected from a group consisting of dispersed red 60, dispersed red 50, dispersed red 146, red scattered 127, scattered red 65, scattered red 86, scattered red 191, scattered red 338, scattered red 302, scattered red 13, scattered red 167 and scattered violet 26.
13. 13. The method according to claim 1, characterized in that the dispersed dyes each are of a group of primary blue color and are selected from the group consisting of dispersed blue 60, dispersed blue 291, disperse blue 118, Terasil blue HLB, also dispersed blue 87 dispersed blue, dispersed blue 56 and dispersed blue 332.
14. 14. The method according to claim 1, characterized in that it further comprises: determining for each selected dispersed dye a characteristic of solidity in light, a characteristic of fading, a characteristic of high humidity of ozone and a characteristic of nitrogen oxide.
15. The method according to claim 1, characterized in that the polyolefin material is continuously dyed by passing the polyolefin material through the dispersed dye mixture solution.
16. 16. A method for dyeing a polypropylene-based fiber, characterized in that it comprises: preparing various dispersed dyeing solutions, each comprising an individual dispersed dye at a concentration of known dyeing; contacting a sample of undyed polypropylene fiber with each of the dispersed dyeing solutions; test each sample of dyed polypropylene fiber to determine its release characteristics; for each of the various dispersed dyes, determine the concentration of maximum dyeing that will produce an acceptable release test; for each of the various scattered dyes within a common primary color group, selecting a plurality of scattered dyes each at least at 75% of its determined maximum dye concentration; combining the selected plurality of disperse dyes to form a first primary color dye mixture of a primary color; preparing a dispersed dye mixture solution of the primary color dye mixture; and contacting the non-dyed polypropylene fiber material with the dispersion dye solution solution at atmospheric pressure to dye the polypropylene fiber.
17. 17. The method according to claim 15, characterized in that it further comprises: testing each sample of dyed polypropylene fiber to determine other solidity characteristics; and from several of the dispersed dyes within a common primary color group, select additional disperse dyes each at a concentration below its determined maximum dye concentration and as a function of its other determined solidity characteristics.
18. 18. The method of compliance with the claim 1, characterized in that each of the plurality of disperse dyes is combined with other dispersed dyes selected at a concentration which, when expressed has a percentage of its maximum dyeing concentration, is within 10% of the percentage of the other the plurality of scattered tinctures with their respective maximum tincture concentration. The method according to claim 15, characterized in that it further comprises: contacting a sample of non-dyed polypropylene fiber with a first dispersed dye solution obtained from a first selected dispersed dye; and after contacting the polypropylene fiber sample with the first dispersed dye solution, contact the stained sample with another solution prepared from a second dispersed dye within the same primary color group as the first dye to test the accumulation ratio of the first tincture and the second tincture; and selecting the first and second dyes for the dyeing mixture as a function of the accumulation ratio test. 20. A dyeing mixture for dyeing a polyolefin material, characterized in that it comprises: a plurality of dispersed dyes within a common primary color group, each of the pluralities of disperse dyes being in a concentration functionally related to its maximum dye concentration individual which will result in an affected release test, a sum of concentrations for the plurality of disperse dyes is substantially greater than the maximum dye concentration determined for each of the individual dyes within the dyeing mixture. 21. The method according to claim 20, characterized in that each of the pluralities of dispersed tinctures is combined with other dispersed dyes selected at a concentration which, when expressed, has a percentage of its maximum dye concentration, which is within of 10% of the percentage of the others of the plurality of scattered tinctures with their respective maximum tincture concentration. The dyeing mixture according to claim 1, characterized in that the selected plurality of scattered dyes each are of a primary yellow group and are selected from a group consisting of dispersed yellow 64, dispersed yellow 23, yellow palanil HM, dispersed coffee 19, scattered orange 30, scattered orange 41, and scattered orange 37, scattered yellow 3, scattered orange 30, scattered yellow 42, scattered orange 89, scattered yellow 235, scattered orange 3, scattered yellow 54, yellow Foron S -6GL and dispersed yellow 233. 23. The method according to claim 20, characterized in that the dispersed dyes each are of a group of primary red color and are selected from a group consisting of dispersed red 60, dispersed red 50, scattered red 146, scattered red 127, scattered red 65, scattered red 86, scattered red 191, scattered red 338, scattered red 302, scattered red 13, scattered red 167, and saw dispersed letal 26. 24. The method according to claim 20, characterized in that the dispersed dyes each are of a group of primary blue color and are selected from the group consisting of disperse blue 60, disperse blue 291, disperse blue 118, blue Terasil HLB, scattered blue 87, scattered blue 148 scattered blue 56, and scattered blue 332. SUMMARY An improved method for dyeing a polyolefin material, and preferably a polypropylene-based fiber, which involves a dispersed dye mixture including a selected plurality of dispersed dyes of the same primary color group. Each dye within the mixture and the concentration of each dye within the mixture is selected by testing individual scattered dye solutions with an unstained sample and determining the maximum dye concentration which will produce an acceptable release test for that dye. A plurality of dispersed dyes within the mixture are each having a concentration of at least 75% of the maximum dye concentration for that individual dye. The selected dye mixture is used to prepare a dispersed dye mixture solution which is then contacted with the polyolefin material to reliably dye the material without problems of fastness. A mixture of red dye, a mixture of blue dye, and a mixture of yellow dye each can be prepared and each can be used separately to dye polypropylene fibers with relatively dark shades without detachment problems. Different proportions of each of the three dye mixtures can be used to dye polypropylene fibers in various selected shades and depths of color.