MXPA99011061A - Method for treating fibrous cellulosic materials - Google Patents

Abstract

Un método para el tratamiento de materiales celulósicos fibrosos utilizando una solución de tratamiento canónico acuosa que contiene un compuesto de polihidroxi cíclico y cloruro de colina, por el cual la absorción del tinte del material, y los efectos ambientales del proceso de teñido subsiguiente son mejorados.

Description

METHOD FOR TREATING FIBROUS CELLULOSE MATERIALS Field of the Invention The invention is directed to a method for the treatment of fibrous cellulosic materials, especially cellulosic fabrics made of cotton and cotton blends, with other fibers such as polyester, nylon, wool, and silk. More particularly, the invention is directed to the treatment of these materials so that both the treatment step and the subsequent dyeing of the materials are more effective and efficient.

Background of the Invention Anionic dyes, such as fiber-reactive dyes and direct dyes, are commonly used to dye cellulose fibers because of their wide range of shades, ease of application, and wet-phase firmness properties suitable for many end-uses. . However, there are certain environmental problems related to the use of such dyes, which occur because large quantities of electrolytes and alkalinity must be used, and the relatively poor absorption of such dyes in the cellulosic fibers. Depending on the method of application, the intensity of the shade and the type of dye, only 70-80% of the dye becomes fixed to the substrate using conventional dyeing methods. As a result, effluents from dyehouses contain an unacceptably high level of unfixed dye, electrolytes and alkaline residues which can cause risks to the environment, and problems of compliance with EPA discharge standards. The problems described above were solved in part by Weltrowski et al in U.S. Pat. No. 5,501,711 by oxidizing the fibers under mild conditions, subjecting the oxidized fibers to reduction with a solution of chitosan oligomers, stabilizing the fibers treated with chitosan by the addition of a reducing agent such as dimethylol dihydroxyethyleneurea (DMDHEU), and then dyeing the fiber thus treated. This process involves 4-5 steps, and even then it does not solve the problems of the firmness of the dyeing and the high cost of the treatment with chitin. This process represents a substantial improvement in the absorption of the dye, and therefore an improved dye output from the dye bath. However, the discharge of metals into the dye bath effluents remains a particularly difficult problem, because many dyes contain substantial amounts of metals. For example, many blue dyes contain copper, and many brown dyes contain chromium. In addition, some dyes contain metals such as cobalt and magnesium. The catalyst traces are still an additional source of metallic contaminants from the dye bath effluents. In addition, certain analogues, such as N-3-chloro-2-hydroxypropyltrimethylammonium chloride, can produce toxic amounts of epichlorohydrin when they are contained in alkaline solutions. Therefore, further improvements are still necessary to improve the absorptions of the dyes, to reduce the electrolyte concentrations in the dyebath, and to reduce the amount and toxicity of the discharge from the dyebath, in each case without sacrifice the dyeing capacity of cellulose fiber. The closest prior art is believed to be WO 96/21767 by Kanzig et al., Process for Dyeing Cellulosic Textile Fabric Materials, and U.S. 4,629,470 from Harper, Process for Dyeing Smooth-Dry Cellulosic Fabric.

Brief Description of the Invention In general, the invention is directed to an improved method for the treatment of undyed fibrous cellulosic material, comprising: 1. A method for changing the surface properties of fibrous cellulose-containing material, comprising: (1) applying to at least one surface of the material containing the cellulose an aqueous treatment solution containing (a) a cyclic polyhydroxy compound selected from the group consisting of dimethyldihydroxy ethyleneurea, dimethylol, dimethyloldihydroxy ethylene urea, trimethylol melamine, hexamethylol melamine and mixtures thereof, (b) choline chloride and (c) a crosslinking catalyst to effect at least 60% by weight of the absorption of the treatment solution on the material, the concentration in the treatment solution of the polyhydroxy compound which is 5-100 g / 1, the concentration of the choline chloride which is 40-600 g / 1 and the ratio or weight ratio of the cyclic polyhydroxy compound with respect to choline chloride which is 0.1 - 6. (2) heat the cellulosic material thus treated from step (1) to a temperature of 121-157 ° C (250-315 ° F) to effect the removal of the water thereof by evaporation, so that the water content is reduced at a level not greater than 1% by weight; 3) further heating the dry material from step (2) to a temperature of 169-240 ° C (320-400 ° F) for 3-180 seconds to effect cross-linking of the cyclic polyhydroxy compound with the cellulose fibers in the material; Y (4) cooling the cross-linked cellulose material.

In one aspect, the invention is directed to a method for treating fabrics containing unstained cellulose, comprising: (1) immersing the tissue in the cationic aqueous treatment solution described above; (2) preheat the fabric from both sides to effect the removal of the water bound therefrom by evaporation; (3) placing the partially dried fabric of step (2) on a dryer or tender frame to effect bidirectional shear on the fabric, and heat the fabric from both sides; (4) cooling the reticulated tissue to a temperature no higher than 66 ° C (150 ° F) by absorbing moisture from the air, until the water content of the tissue is in equilibrium with the cooling air; Y ) remove the fabric from the tender frame either between steps (3) and (4), or after step ().

In a second aspect, the invention is directed to a method for improving the dyeing of cellulosic tissues by treating the tissue as described above, and coloring the tissue thus treated with an anionic dye selected from the group consisting of acidic dyes, the dyes reactive with the fibers, and the mixtures thereof to effect at least 90% by weight of the dye output from the dye bath. In a still further aspect, the treatment process described above is applied to papermaking.

Brief Description of the Drawing The drawing consists of a single Figure, which is a schematic representation of the method for finishing tissues containing cellulose according to the invention.

Definitions Whiteness is measured by test method 110-1889 of the AATCC. The term "cellulosic fiber" refers to fabrics that contain at least 25% cellulosic fibers such as cotton, and blends or combinations of cotton with polyester, wool, nylon, and rayon. When used herein, the term DMDHEU refers to the dimethylol dihydroxyethyleneurea compound and the glycolated or methoxylated analogs thereof.

"K / S" refers to the ratio of the absorption coefficient (K) to the dispersion coefficient (S) as measured on a tissue by reflectance spectrophotometry. For a particular wavelength of light, the ratio is defined by the Kuberka-Munk function, K / S = (1-R) / 2R, where R is the reflectance of a sample at the particular wavelength. The term "dye output" refers to the% by weight of the dye which has been removed from the initial amount of the dye in the dye bath. The term "owf" means "on the weight of the fiber", based on the dry weight of the fiber. The term "moisture outlet" - is a measure of adsorbency on a tissue, and is defined as the time (in seconds) required for a drop of water placed on the surface of a tissue to disappear by adsorption on the tissue. The term "prepared tissue" refers to tissue which has been desized, scoured, bleached, and / or mercerized.

Detailed description of the invention Composition of the Treatment Bath: The treatment bath for use in the invention (the mordant impregnation bath in the treatment of tissues) is comprised of (1) a cationic reactive component, (2) a cellulose crosslinking agent , and (3) a catalyst for the crosslinking agent. In the treatment of tissues, the mordant impregnation bath may also contain one or more of the anionic or nonionic softening agents, a wetting agent, an anti-migration agent, and a non-ionic or cationic stain release agent. It will be recognized that the application of the treatment composition can be carried out in several other ways. For example, in the case of fabrics, the material can be immersed in the treatment solution so that it can be applied by means of contact with a soft contact roller or an engraved roller. Other coating techniques with a liquid, such as spraying, can also be used. For the purposes of the invention, the cationic reactive agent is choline chloride. It has been observed that choline chloride reacts chemically with the cyclic polyhydroxy compound, but not with the fiber. In the case of DMDHEU, this reaction is believed to be as follows: ? c Cl + (1) HOCHrN N-CH2OH i i HOCH2-CH2-N- (CH3) 3 Cell-OH HO-C- -C-OH I I H H 0 II? Cl (2) CeIl-O-CH NN-CHO-CHrCH N- (CH3) 3 i I + 2H2O HO-C- C-OH H H It has been observed that an absorption of the non-ionic dye is increased when more choline chloride is reacted with DMDHEU. However, to balance or balance the absorption of the dye with the shrinkage control, it is preferred to use 2-4 parts by weight of choline chloride by weight of DMDHEU. Although it is not known with certainty, choline chloride appears to function as a lubricant or softening agent for fiber. In addition, choline chloride is very resistant to yellowing, and therefore helps to retain the whiteness of the treated tissue.

The cyclic polyhydroxy compound, of course, serves as a crosslinking agent for the cellulose in the fibers. In this paper, it is not essential to achieve a high color absorption; however, its use is preferred because of its beneficial effect on reducing the shrinkage of the treated tissue. A further advantage of the invention is that various visual effects can be applied to the fabric. By varying the ratio of DMDHEU to choline chloride, the "heather or mottled thread" and the "clean look" can be achieved while still retaining the good qualities of washing, fading and light firmness in the fabric. For example, a weight ratio of choline chloride / DMDHEU of 1/6 and 0.5% by weight of the Catalyst, and a 65-70% complete "cleaning" of the dye can be obtained. On the other hand, at a ratio of approximately half the weight, the dyed fabric is firm in color. At least 5 g / 1 of the cyclic polyhydroxy compound are necessary in the treatment bath to obtain good shrinkage control. At least 10 g / 1 of the cyclic polyhydroxy compound are preferred. However, more than 100 g / 1 of the cyclic polyhydroxy compound are not desirable, so that the tensile strength is not decreased. It is interesting to note that choline chloride mitigates the adverse effect of the higher concentrations of cyclic polyhydroxy materials. Therefore, they can be used in high quantities. For best results, the weight ratio of the polyhydroxy compound to choline chloride needs to be only 0.1-6. It is preferred to use at least 10 g / 1 of choline chloride in the mordant impregnation bath, but not more than 300 g / 1 should be used to avoid any adverse reaction of the choline chloride with the polyhydroxy compound. Suitable crosslinking catalysts for use in the treatment bath are acid catalysts such as magnesium chloride, zinc nitrate, aluminum sulfate, and mixtures thereof. An essential component of the mordant impregnation bath is the crosslinking catalyst which causes crosslinking of the cellulose in the fabric. At least 1 g / 1 of the catalyst is required to adequately crosslink with the fabric, and thereby improve its fabric stability, for example shrinkage. However, no more than 50 g / 1, and preferably no more than 40 g / 1 of the catalyst should be used. The reason for this is that the excess catalyst causes the hydrolysis of the cellulose, which leads to the loss of the tensile strength of the fabric. It is interesting to note that at equivalent levels of the catalyst, the color intensity during dyeing is enhanced by higher levels of choline chloride. This phenomenon is shown by the data in Table 4 below. Although cyclic polyhydroxy compounds, choline chloride and catalyst are the essential components of the treatment solution, other materials will need to be added to cause particular changes in the properties of the treatment bath. For example, migration of the dye from the fibers of the fabric can also occasionally be a problem. This is, in large part, the result of the low viscosity of the mordant impregnation bath. Therefore, since the mordant impregnation bath of the invention can not contain any significant amount of the dissolved polymer, it will often be desirable to raise the viscosity of the impregnation bath with the mordant by either of two methods. The first way to increase the viscosity of the bath is to reduce the water content. This can be done by applying a vacuum to the fabric coming out of the pressed rollers on the outlet of the mordant impregnation bath. The second procedure is to add a water-soluble polymer to the impregnation bath with the mordant. It will be recognized that both methods of increasing viscosity can be used together. Polymers suitable for this purpose include poly (acrylic esters), block copolymers of mannuronic and guluronic acids. Stain release agents are usually not necessary for cotton fabrics. However, they will be necessary for mixtures with high polyester / cotton content. When used in the invention, suitable stain release agents include materials such as polyethylene glycols, methacrylic acid copolymers and ethyl acrylate, and fluoroacrylic polymers. However, the materials must be either non-ionic or cationic to avoid precipitation of choline chloride. Other additives which can be used with the invention in the impregnation bath with the mordant include anionic or non-ionic tissue softening agents or anionic or nonionic wetting agents. Suitable softening agents include non-ionic fatty glycerides and polyethylene emulsions. Suitable wetting agents are non-ionic detergents, such as the hydrophobe of ethoxylated linear alcohol C 2 -3, and the product of the reaction of 2,6,6-trimethyl-4-nonanol and ethylene oxide. Such materials are well known in the art of finishing or finishing, and can be used with the invention in a manner similar to their use in conventional non-cationic finishing processes. For some application methods, it is preferred to add a transient dye or other ultraviolet ray absorber to the treatment solution to facilitate visual observation of the regularity with which the treatment solution is applied. This is especially contemplated to observe with certainty the pressure of the padded rollers, the soft contact rollers, the etching rollers with acids, etc. In the absence of the catalyst, the primary components of the treatment solution are stable and do not suffer significant reaction when the solution is stored at ambient temperatures. Accordingly, the aqueous solutions of the cyclic polyhydroxy compounds and the choline chloride can be prepared in advance for later use. Such premixed compositions are comprised of (a) cyclic polyhydroxy compounds, (b) choline chloride and the remainder (c) water. The weight ratio of (a) to (b) should be within the range of 0.1-6, which corresponds to the useful proportions of these components in the treatment bath. However, the concentration of these active components in the solution can vary widely. Although small solution concentrations can be used, more concentrated solutions are cheaper. Accordingly, it is preferred that the active components be at least 40% by weight and preferably 60% by weight or even higher. However, to avoid problems of viscosity during the treatment of cellulose, it is preferred that the concentration of the active components does not exceed about 80%.

Operational Variables of the Finish: In the finishing operation, the fabric must have a wet phase absorption of 50-75% by weight. The dyeing is carried out at 121-196 ° C (250-385 ° F), and the curing is carried out at 121-204 ° C (250-400 ° F). In this process, the fabric will typically absorb 3-8%, of the weight on dry basis, of the finishing chemicals. The curing time and the temperature used in the process of the invention, of course, will vary according to the physical properties of the fabric. Accordingly, they will be different for different combinations of the fibers. As a whole, higher curing temperatures will require shorter cure times. However, some tissue mixtures are more sensitive to thermal degradation. For example, the curing temperature of the wool blends will be kept well below 177 ° C (350 ° F), preferably below 166 ° C (330 ° F), to avoid damage to the wool fibers. A temperature of approximately 163 ° C (325 ° F) is still further preferred. It is preferred in the practice of the invention to remove substantially all of the water before curing the fabric. Therefore, it is preferred to dry the tissue at a lower temperature so that premature crosslinking, which could be prevented after water removal, is not carried out. Accordingly, during drying, the temperatures should not exceed 160 ° C (320 ° F), and preferably not more than 149 ° C (300 ° F). However, during the crosslinking step, the temperature can be as high as. 204 ° C (400 ° F), provided that the curing temperature does not exceed the thermal degradation temperature of any mixed fiber contained in the fabric. As mentioned above, the drying and curing steps are a function of both time and temperature. The higher the temperature, the shorter the time needed for drying and curing. For example, during curing of the fabric treated with the mordant bath, if a temperature of 160 ° C (320 ° F) is used, then the curing time should be about 2 minutes to cure the tissue completely. On the other hand, if a temperature of 204 ° C (400 ° F) is used, only 3 or 4 seconds are necessary. It will be recognized by those skilled in the art that it is necessary to heat the blends or cotton / polyester blends of the assembly. This function, of course, can be carried out during the mercerization, before the bath with the mordant or before the dyeing. However, an advantage of the invention is that the adjustment or hardening by heating is carried out completely in the step of curing the process. Accordingly, no additional steps or additional equipment are required to achieve the heat setting or hardening of such cotton / synthetic fiber fabrics. When the fabric that is treated by the process of the invention is going to undergo dyeing, it is essential that the fabric be prepared to avoid interference with the absorption of the dye in the fabric.

Composition of the Dye Bath: An important feature of the mordant bath step of the invention is that it does not require any operational change in the subsequent dye bath. Accordingly, the fabric / liquor ratio (F / L) will usually be within the range of 1: 5-1: 40, and conventional dye bath temperatures will be used, for example, 60 to 115 ° C (140-239). ° F). All anionic dyes can be used in dyeing fabrics which have been prepared according to the invention. However, the dyes listed in Table 1 are preferred.

Table 1 In Table 1 above, the dyes and their sources are identified by the following registered trademarks: Registered Trademark Owner Acidol Badische Anilin & Soda Fabrik A.G. (BASF) Ludwigshafen / Rhine, FRG Basilen BASF Cibacron Ciba-Geigy Corporation New York, NY Intralight Crompton & Knowles Corporation New York, NY Palantin BASF Remazol Hoechst, A.G. Frankfurt / Main, FRG Sumafix Mitsubishi K.K., Tokyo, Japan Superligth Crompton & Knowles Corporation In addition to the dyes described above, the sulfur, vat, and azoic dyes can be used for coloring the fabrics which have been treated according to the invention. The sulfur and vat dyes are anionic in their leuco form and the azo dyes are anionic due to the presence of the sulfonic salt groups in the molecule. Operational Variables of the dye bath: The dye bath in which the prepared fabric is colored will usually contain water, the dye, the leveling agent, the wetting agent, and the defoamer. For use with organic coloring matters, such as those used in this invention, the wetting agents must be non-ionic or anionic. Polyethylene glycol (mono-octylphenol) ether is useful for this purpose. In the course of agitation, such as that which is found in dyeing by means of a jet, a microfoam can be produced. Such foaming can be eliminated by adding to the dyebath a small amount of the nonionic defoaming agent, such as 0.1-0.2% by weight of the silicone polymer.

In order to moderate the rate of escape of the dye, it will often be desirable to add a small amount of a leveling agent to the dyebath. These materials form an intermediate complex with the coloring material which facilitates the migration of an unfixed coloring material to the less concentrated areas. Although the proportions of these essential components will vary widely according to the fabric, the exact nature of the finishing treatment and the composition of the dye will normally be present in the following proportions, owf: Dye 0.1-4% Leveling agent 1-3% Moisturizing Agent 0.1 - 1.0% Defoaming agent 0.1 - 0.3% An additional operational critical variable in the dyebath is the tissue / liquor weight ratio, which will usually be within the range of 1: 5 to 1:40. The temperatures of the dye bath will be at least 66 ° C (150 ° F), and preferably 93-96 ° C (200-205 ° F). The time within the dye bath will usually be a function of the degree of absorption of the dye which is desirable. Of course, it is a major advantage of the invention that the time required to achieve the high output levels of the dye be greatly reduced. Referring now to Figure 1, the treatment of the cellulosic tissues according to the invention will commonly be carried out in the following continuous manner: The previously prepared fabric (desprestado, bleached and mercerizado) that is going to be pretreated, is provided on a roller 1 of feeding the fabric from which it is stretched to the scarf 3, comprising a trough and two rollers of pressed. The pad 3 contains a bath of cationic treatment solution 5, through which the tissue is passed, and absorbs a quantity of the treatment solution. Leaving the treatment bath, the fabric is passed between the depressed rollers 7a and 7b to remove the excess treatment solution removed from the tissue. The fabric, which contains the treatment solution both unbound and absorbed, is passed from the press rollers 7a and 7b to the extractor with vacuum grooves 9, in which the fabric is subjected to the force of a vacuum from below to remove the unbound treatment solution contained in the tissue. The tissue left by the extractor with vacuum grooves 9 contains approximately 50% by weight of the owf treatment solution. From the vacuum groove extractor 9, the fabric is passed to the infrared dryer 11, in which the fabric is heated vertically on both sides at a temperature of at least 121 ° C (250 ° F.) to effect the removal of unbound water down to a level of 5-20% owf. Temperatures as high as 157 ° C (315 ° F) are frequently used for this purpose. Of course, it is necessary to retain at least 5% by weight of the moisture in the fabric to maintain an adequate degree of swelling of the fiber, which is necessary to control the uniformity and width of the fabric. It is preferred, however, that the fabric that is introduced into the tender frame contain no more than about 20% by weight of water to make the process more efficient. A humidity level of 10-15% is preferred. It should be noted that the "most desirable moisture content for the fabric will vary according to the kind of fabric being treated, and the degree of pretreatment." The heated fabric is removed from the infrared dryer 11 and passed to the tender frame. Annex 13, in which the fabric is placed on hooks to apply a bidirectional shearing force to the fabric, the fabric thus supported is then subjected to heating on both sides of the fabric by the hot air, and the temperature of the fabric is raised to a level of 121-204 ° C (250-400 ° F) .The speed of the fabric through the laying frame 13 to about 177-204 ° C (350-400 ° F) is about 45.7-68.6 m / min (50-75 yards / minute) It is necessary to gradually cool the fabric when it leaves the tender frame and before it is rolled up to minimize additional chemical reactions in the fabric while it is wound up. So, in the extr Emo running down the tender frame, the fabric is cooled with air to approximately ambient temperature, and the fabric is wound onto the cylinder for storage of the fabric 15 before subsequent drying. While leaving the cooling section of the tender frame, the water content of the fabric is in approximate equilibrium with the cooling air, for example about 8-10% by weight. It will be recognized that the treatment solution can be applied to the fabric by different techniques of the bath for the application of the mordant, such as coating with a roller, using either printed rollers or soft contact rollers. The treatment solution can be applied to one or both sides of the fabric by the use of one or two rollers respectively.

When the treatment solution is applied by means of a mordant bath (by submerging), the capacity of the treatment solution will usually be higher than that when it is applied by the coating with the roller. Accordingly, the concentration of the ingredients of the treatment solution is higher for mordant bath applications. An important variable in the application of the mordant and the dyeing of the tissues, is the effect of the bath of the mordant on the whiteness of the fabric. The fabric that is prepared by the invention is preferred to have a whiteness of at least 60 to ensure a consistent color. An important advantage of the invention is that it does not have a detrimental effect on the whiteness of the treated fabric. In fact, the use of choline chloride in the application step of the mordant seems to reduce the yellowness caused by other components of the mordant bath. Catalysts and polymers are frequently problematic in this regard. Therefore, when desirable, the whiteness of the fabric can be retained at a level of 80-90 only by adjusting the residence time and the temperature of the fabric within the framework of laying. In particular, by decreasing the temperature and / or residence time within the framework of laying, the degree of whiteness can be retained at such higher levels. The invention, therefore, is useful for treating woven, non-woven and knitted fabrics and items made therefrom, as well as yarn and yarn for use in the manufacture of fabrics. In addition, the invention can be used for the treatment of other substrates containing cellulosic fibers, such as wood pulp, and paper. When the invention is applied to the paper treatment, it can be carried out in any of three different places in the papermaking process. That is to say, the treatment solution can be added to the process before the formation of the sheet either in the beater or in the upper box. However, the treatment solution can also be applied to the paper after the formation of the sheet in a manner analogous to the treatment of the tissues as described above.

EXAMPLES Example 1 A 100% prepared cotton fabric is pretreated at room temperature with a cationic treatment solution having the composition given below. In addition, a similar amount of the same fabric was pretreated in the same manner, except that the choline chloride was omitted from the composition for comparison purposes: DMDHEU (70% solution) 40 g / 1 Choline chloride (70% aqueous solution) 100 g / 1 MgCl2 catalyst (25% aqueous solution) 40 g / 1 Softener (25% ac solution) 10 g / 1 Non-ionic wetting agent (100%) 0.5 g / 1 Absorption of the treatment solution by the tissue was 70% owf, after which the treated tissue was dried at 121 ° C (250 ° F) for two minutes, and then cured at 191 ° C (375 ° F). ) during a minute.

Example 2 Separate amounts of the pretreated tissues of Example 1 were then stained with 10 GL Blue of Solophenyl, and Blue CR of Cibacron, a dye reactive with the fiber, to observe the dye output from their respective dye baths. The fabric was dyed with a jet at a ratio of the fabric with respect to the 1:20 liquor, the dye materials both direct and reactive with the fiber were used in the bath at a level of 3% owf. For direct dyeing of the unfinished fabric, the dyebath contained 180 g / 1 of common salt and, for dyes reactive with the fiber, the dye bath contained 4 g / 1 of soda ash, 100 g / 1 of common salt, and 1 g / 1 NaOH. For the dyeing of the pre-finished fabric, chemical substances were not necessary and therefore they were not added. The dyeing results are given in Table 2, which follows Table 2 STUDY OF DYE EXIT The data in Table 2 show that 90% of the absorption of the dye for cationically pre-finished fabrics required only 90 minutes, while the time to achieve 90% of the dye absorption for the untreated tea was 175 minutes for direct dye, and 245 minutes for fiber-reactive dye. Although only nominally, 90% absorption of the dye was achieved by the tissues, which have not been pretreated according to the invention, a substantially complete absorption (100%) was achieved for those tissues which have been pretreated in the manner of the invention.

Example 3 Using the same cationic treatment procedure as described in Example 1, a series of pre-finishing tests were carried out, in which the relative proportions of choline chloride, DMDHEU and catalyst were varied to determine the relative effectiveness of such solutions. The tests were carried out at 6 and 8% owf chemical addition levels. The shrinkage of the fabric after washing in the laundry, the tensile strength and tear resistance were measured on the tissue sample. The results are given in Table 3, which is given below.

Table 3 EFFECT OF THE RELATION OR PROPORTION OF CHLORIDE CHLORIDE AND OF DMDHEU AND DIMENSIONAL STABILITY OF AGGREGATE TISSUE (SHREDDING OF LAUNDRY), PHYSICAL PROPERTIES Cor_entración in weight of the water. By comparing Examples 1 and 2, 4 and 5. and 8, and 10 and 11, it is observed that the increase in the amount of choline chloride in each case led to a reduced amount of shrinkage of the tissue, and both the Tensile strength such as tear resistance were improved. This was true in the addition to both 6% and 8%. These data do not show that the use of higher amounts of catalyst causes at least minor damage to shrinkage, tensile strength and tear resistance. For example, compare test numbers 8 and 11 and test numbers 9 and 12. For comparison purposes, it should be noted that the acceptable levels of tensile strength and tear strength are 6.3 kg (14 pounds) and 8.6 kg (19 pounds), respectively. The dye absorption and color fastness of all the previous examples were satisfactory, but Samples 2 and 11 had the best dye absorption and color fastness.

Example 4 Using the same procedure as in the previous examples, a series of tests was carried out to observe the effect on the yield of the maximum dye of the ratio of choline chloride, DMDHEU and the level of the catalyst. The results of these tests are given in Table 4 below.

Table 4 CORRELATION OF TENDER PERFORMANCE WITH HILL CHLORIDE RELATIONSHIPS, DMDHEU, AND CATALYST LEVEL Percentage of chemical addition to 6% owf. K / S »rr? Entts higher number, higher tissue yield * CC = Chloride (Tolina) The K / S values in the above table indicate the highest dye absorptions which are available from the invention. For example, the use of choline chloride alone gave very low K / S values, and the use of the catalyst in addition to choline chloride gave some improvement. However, when the DMDHEU was also added, the K / S values were many times higher.

Example 5 An additional series of tests was carried out to observe the effect of the drying and curing conditions (time and temperature) on the dye yield. The proportions of the treatment solution were 150/100/40 choline chloride / DMDHEU / Catalyst. Measurements were made on 100% pre-finished, cationic cotton fabric, which has 6% owf of dye absorption. The dye yield is measured by the K / S value, ie the total wavelength / average wavelength, of each specimen. These data are given in Table 5 below: Table 5 EFFECT OF DRYING AND CURING ON THE PERFORMANCE OF DYE These data show that by varying the temperatures, the drying and curing steps can be carried out satisfactorily on either a single step or two steps. In particular, the data show that a temperature of 177 ° C (350 ° F) for 1 minute was insufficient to give a satisfactory dye absorption, but when the time was raised from 1 minute to 2 minutes, the absorption of the dye as indicated by the K / S values rose to a usable level. However, the use of two steps, which is the use of different temperatures for drying and curing, produced significantly higher K / S values. The maximum K / S values were obtained when the drying was carried out at 138 ° C (280 ° F) for 2 minutes, and the curing was carried out at 193 pcs (380 ° F) for 1 minute.

Example 6: A large-scale commercial cationic dyeing and pre-finishing test was carried out, using 182.88 m (200 yards) each of 3/1 twill, 100% cotton, and Oxford cloth, 100% cotton. The dyeing is carried out in a commercial scale jet dye, using several combinations of two or three different dyes. The tissues of objects were processed in a pad at 21 kg / cm2 (30 psi) at a speed of 22.9 m / min (25 yards per minute) using a two-roll depressed cylinder. The absorption of the liquid was approximately 70-75% on a wet basis. Foulard processed fabrics were dried at 138-143 ° C (280-290 ° F) for 140 seconds on a 175 mm (69 inch) tender frame assembly. The dried fabric was cured on the same laying frame at 185 ° C (365 ° F) for 35-40 seconds. The prefinished fabric was then dyed on a Gaston County jet dyeing equipment at a tissue / liquor ratio of 1:25. -From 4-5 kg of fabrics were dyed with various combinations of dyes to evaluate the uniformity of the dyeing of the tissues, the development of the tone and the firmness of the color. The composition of the mordant application bath was as follows: 120 g / 1 Choline chloride (70%) 60 g / 1 Fixapret ECO (70%) 30 g / 1 Catalyst HC ig / i Siligen NB 250 (softener) 1 g / 1 Basapon LN (wetting agent) Rest Total water: 1000 g The dye compositions are given in Table 6 below.

Table 6 COMBINATIONS OF COLORING MATTERS All fabric dyes had good appearance for commercial acceptance with excellent washing, fading (rubbing), and firmness of light. The results are given in Table 7, which is given below: Table 7 FIRMNESS OF THE COLOR OF TEST TISSUES In the above data, a mark of 5 is the best. A trademark of 3 is a commercially acceptable minimum. All brands or evaluations are based on the AATCC scale, which is based on the Gray Scale. (1) 49 ° C (120 ° F), 45 minutes with detergent only. This test is a measure of color leakage or loss of color; (2) This test is a measure of the rub resistance, ie the loss of color due to the loss of dye from abrasion; It is noted that in relation to this date the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following

Claims (19)

1. A method for changing the surface properties of a fibrous cellulose-containing material, characterized in that it comprises: (1) applying to a surface of the cellulose-containing material a cationic aqueous treatment solution containing (a) a heterocyclic polyhydroxy compound selected from the group consisting of dimethyldihydroxy ethyleneurea, dimethyloldihydroxyethyleneurea, trimethylol melamine, hexamethylol melamine and mixtures thereof, (b) choline chloride and (c) cross-linking the catalyst to effect at least 60% by weight of the absorption of the treatment solution on the material, the concentration in the treatment solution of the polyhydroxy heterocyclic compound which is 5-100 g / 1, the concentration of choline chloride which is 40-600 g / 1 and the weight ratio of the polyhydroxy heterocyclic compound to choline chloride which is 0.1-6; (2) heat the cellulosic material thus treated from step (1) to a temperature of 121-157 ° C (250-315 ° F) to effect the removal of water therefrom by evaporation, so that the water content is reduced to a level no greater than 1% by weight; (3) further heating the dry material of step (2) to a temperature of 169-240 ° C (320-400 ° F) for 3-180 seconds to effect cross-linking of the cyclic polyhydroxy compound with the cellulose fibers in the material; Y .4) cooling the crosslinked cellulosic material.

2. The method according to claim 1, characterized in that the fibrous cellulose-containing material is a prepared non-dyed fabric.

3. The method according to claim 2, characterized in that it comprises: (1) immerse the tissue in the cationic aqueous treatment solution and remove the tissue therefrom; (2) preheat the fabric from both sides to effect the removal of the water bound therefrom, by evaporation; (3) placing the dried fabric partially from step (2) on a dryer or tender frame to effect or carry out the shear stress on the fabric, and heat the fabric from both sides; (4) cooling the reticulated tissue to a temperature not higher than 66 ° C (150 ° F) to effect the absorption of moie from the air until the water content of the tissue is in equilibrium with the cooling air; Y (5) removing the fabric from the dryer or tender frame, either between steps (3) and (4) or after step (4).

4. The method according to claim 2, characterized in that the treatment solution is applied to at least one surface of the non-dyed fabric prepared by means of soft contact rolls or engraved rolls.

5. The method according to claim 2, characterized in that the fabric contains at least 25% owf of cellulose.

6. The method according to claim 2, characterized in that the fabric has a humidity output of less than 3 seconds.

7. The method according to claim 6, characterized in that the fabric contains a wetting agent.

8. The method according to claim 7, characterized in that the wetting agent is cationic.

9. The method according to claim 7, characterized in that the wetting agent is nonionic.

10. The method according to claim 2, characterized in that the treatment solution contains a tissue softening agent.

11. The method according to claim 2, characterized in that the cellulose-containing fabric is a polyester / cotton blend and the treatment solution contains a stain-releasing agent.

12. The method according to claim 2, characterized in that a vacuum is applied to one side of the wet fabric between steps (1) and (2) to reduce the free water content thereof to a level of 40-60% owf. .

13. The method according to claim 2, characterized in that the fabric is selected from the group consisting of woven, non-woven fabrics and knitted fabrics.

14. The method according to claim 1, characterized in that the cellulose-containing material is for use in the manufacture of paper.

15. The method according to claim 14, characterized in that the treatment solution is applied by the addition of the treatment materials to the contents of the beater box before the formation of the paper sheet.

16. The method according to claim 14, characterized in that the treatment solution is applied by the addition of the treatment materials to the contents of the upper box before the formation of the paper sheet.

17. The method according to claim 14, characterized in that the treatment solution is applied after the formation of the paper sheet. .

18. The method according to claim 1, characterized in that the treatment solution is applied to the yarn containing the fibrous cellulose by submerging the yarn in the treatment solution.

19. A method for improving the dyeing characteristics of tissues containing cellulose, characterized in that it comprises treating the tissue in the manner described in claim 2 and coloring the tissue thus treated with an anionic dye selected from the group consisting of acidic dyes, dyes reagents with the fibers, direct dyes and mixtures thereof to effect at least 90% by weight of the dye output from the dye bath.