ITMI20130720A1 - DYEING PROCESS FOR DYEING OF A HEAD WITH PROTEIN FIBERS - Google Patents

Description

F1.G0064.12.IT.1 Dr. Guido PONTREMOLI (Register n.1397 B)

1

DESCRIPTION

Attached to a patent application for INDUSTRIAL INVENTION having the title

â € œPROCESS FOR THE DYEING OF A GARMENT MADE WITH

5 PROTEIN FIBERS, WITH DENIMâ € EFFECT

On behalf: Massimo Guarducci S.r.l.

Via Toscana 29 / 29A

59100 PRATO PO

Authorized representatives: Dr. Guido PONTREMOLI, Registered register. nr. 1397 B, Ing. Dario ALDE, Registered register nr. 1338 B, Eng. Marco BELLASIO, Registered register nr. 1088 B, D.ssa Cristina BIGGI, Registered register nr. 1239 B, Dr. Michela ERRICO, Registered register nr. 1520 B, Ing Mario GIRLANDO, Registered register nr. 1514 B, Ing. Simona INCHINGALO, Registered register. nr. 1341 B, Ing. Giancarlo PENZA, Registered register nr. 1335 B, Elio Fabrizio TANSINI, Registered register nr. 697 BM, Ing. Luigi TARABBIA, Registered register nr. 1005 BM, Dr. Bartolomeo TIRLONI, Registered register nr. 1207 B, Eng. Lucia VITTORANGELI, Registered register No. 983 BM

*; The present invention refers to a process for dyeing an article made with a protein fiber, capable of giving the final product a visual appearance of the Denim type, by reaction with 10 sulphamic acid. The partial treatment with sulfamic acid, carried out before dyeing, gives the product a partial resistance to the dye itself and such that it assumes the appearance of denim, characteristic, for example, of jeans as illustrated in figure 1. ;; 15 State of the art The dyeing process of a textile material generally takes place through the passage of the material (fiber, yarn or fabric) in an aqueous solution of the dye. This step ends with the fixing F1.G0064.12.IT.1 Dott. Guido PONTREMOLI (Register n.1397 B) ;;; 2 ;; of the dye on the dyed support, generally by bonding or chemical interactions between the molecules of dye and the molecules or functional groups of the fiber. The dyeing processes used in the state of the art are various. For example, you can dye the fiber and then proceed to spinning and weaving, or you can dye the yarn already made and then proceed to weave. Finally, as an alternative to the two types of dyeing mentioned above, the material can be dyed in the final stage, on the fabric already made. This type of process is commonly called â € œpatch dyeingâ €. ; 10 Among the garments made by dyeing the yarn, the denim fabric (and the consequent denim effect) is one of the most well-known and used textile materials all over the world, especially in the characteristic blue shade. This fabric is characterized by a twill weave in three (2: 1), with a diagonal striping, distinguishable above all by its typical look of jeans. ; 15 Another effect that uses yarn dyeing, but which is different from the denim effect as indicated above, is the so-called â € œmelangeâ € effect or aspect. This aspect is generally obtained by mixing together completely dyed fibers and colorless fibers, joined together in a regular way or not according to the visual effect â € œmelangeâ € to be obtained. ; 20 To date, the denim effect is generally obtained by using yarn-dyed cotton fibers or, rarely, by printing on fabric. There remains therefore the need to find a procedure for obtaining a denim effect by dyeing the fabric, in particular as regards protein fibers and in particular for wool. 25 The applicants have surprisingly found that when a textile material containing protein fibers is only partially reacted with sulfamic acid, the subsequent dyeing step, for example with an anionic dye, allows to obtain a final product characterized by the desired denim effect, attributable to that associated with the best known 30 cotton denim fabric. ; F1.G0064.12.IT.1 Dr. Guido PONTREMOLI (Register n.1397 B) ;;; 3 ;; In general, the dyeing process, whether fiber, thread or fabric, involves the dissolution of a dye in an aqueous bath, and the subsequent transfer and fixing of the dye from the bath to the chosen textile support. In this regard, the expert in the sector is aware of the fact that depending on the nature and / or type of support, it is necessary to choose precise classes of dyes, based for example on the chemical nature of the compounds or of the chemical interactions that are created between the material to be dyed and the dye. In fact, different types of fibers are available (for example natural, synthetic, protein, mineral and the like) which, due to their chemical nature, may require the use of chemical dyes having suitable structures and chemical behavior. ; The protein fibers are usually dyed with anionic dyes of the acid, metal-complex or reactive type, which thanks to their chemical nature are able to interact with the groups of the protein fiber made positive at pH 15 lower than about 4 (known in the sector as isoelectric pH), allowing to obtain dyes with high fastness to light, rubbing and water. Protein fibers are typically those fibers of animal origin that possess a structure formed by protein chains, made up of a series of natural amino acids. ; 20 Examples of protein fibers are wool (consisting of proteins with a high keratin content) and silk (consisting of fibroin and sericin), which have the characteristic free -OH and â € “NH2 groups. These hydroxyl and amino groups are in fact the main responsible for the interactions and bonds that are established between the protein fiber and the dye. ; 25 The latter has one or more anionic groups which at pH lower than 4 are able to react with the â € “OH and â €“ NH2 groups present in the dye bath in protonated form, binding stably to the fiber. ; This interaction has also been studied and used to optimize dyeing so-called â € œresistanceâ € processes, in order to make a partial dyeing of the protein fiber, in order to obtain particular F1.G0064.12.IT .1 Dr. Guido PONTREMOLI (Register n.1397 B) ;;; 4 ;; drawings or visual effects resulting precisely from the partial interaction between fiber and dye. Among the best known methods to increase the dyeing resistance of protein fibers, the use of sulfamic acid (NH2SO3H) or 5 sulfuric acid is known. As described for example in US2726133, sulphamic acid is able to react with the free groups of the fiber -OH and - NH2 (i.e. at the binding sites with the dye), leading to the formation of the corresponding - - groups - OSO3e - NHSO3. Due to their chemical nature, these latter functionalized groups are no longer able to bind to the commonly used anion dye. As a result, when a textile material or a derivative of protein fiber, typically wool, is treated with sulfamic acid, the chemical transformation of the reactive sites of the substrate is such that the dyeing process with anionic dyes is inhibited and the support is essentially be 15 intingible. ; Cameron et al. (â € œReaction of wool with sulfamic acidâ €, Textile Research Journal, pages 619-624) describe a process of functionalization of a wool fiber with sulfamic acid, including a first step of impregnation and the subsequent heat treatment. In particular, the 20 authors conclude that when the treatment takes place at a temperature of 150-160 ° C for at least 4 minutes, the resulting fiber shows almost complete resistance to dyeing. In other words, when the wool fiber is impregnated with sulfamic acid and subjected to the above heat treatment, the material is intingible with the normal dyes 25 used for wool. To demonstrate that the fiber has reacted with sulfamic acid, the authors use the barium chloride test, as reported for example in Mease et al. â € œdetermination of sulfur and sulfate in woolâ €, Bur. Stand. J. Res 13, 617 (1934). ; F1.G0064.12.IT.1 Dr. Guido PONTREMOLI (Register n.1397 B) ;;; 5 ;; In practice, the wool fiber is impregnated in an aqueous bath containing 20% of sulphamic acid, 20 % urea and a wetting agent, for 30 minutes at 40 ° C. It is then dried at 80 ° C. The fiber is then treated at 150-160 ° C for 4-5 minutes. 5 At the end of the temperature treatment, the% of free (ie unreacted) sulphamic acid present on the fiber is determined, for example by the method described by Barritt et el in (2). On the other hand, to determine the% of sulphamic acid actually bound to the fiber, the textile material is hydrolyzed with HCl, and the subsequent precipitation treatment of the hydrolyzate with BaCl2 is then carried out. In this way, the sulphamic acid present on the fiber (both the bound and the unfixed one) will precipitate in solution as barium sulphate. By subtraction with the free acid calculated first with the Barrit method, the% by weight of acid which was actually bound to the fiber is then determined. ; From the calculations, it appears that the fiber is able to bind with sulfamic acid for 12% of its weight. This means that the free sites responsible for the change in dyeing behavior occupy the fiber for about 12% of its weight. From the results indicated it is therefore concluded that when the 20 quantity of sulphamic acid reacted with the fiber (as calculated above) is equal to 12%, the fiber is to be considered saturated and substantially intingible with most of the dyes commonly used for the dyeing of protein fibers. Applicants have now found that when a woolen fabric is partially functionalized with sulfamic acid, a denim effect can be achieved by dyeing operations known in the art. In this regard, by partial reaction of the wool fabric with sulphamic acid we mean a reaction between substrate and acid such that only a certain percentage, less than 12%, of the -OH and -NH2 groups of the fiber 30 reacts with the acid. ; F1.G0064.12.IT.1 Dr. Guido PONTREMOLI (Register n.1397 B) ;;; 6 ;; Therefore, the invention refers to a dyeing process of a product containing protein fibers, preferably of wool, to obtain a denim effect, said process which comprises: wetting agent, and b) subsequent dyeing with an anionic, reactive or metal complex dye. In a further aspect, the invention refers to a manufactured article, 10 preferably of wool, having a denim aspect obtained with the process of the present invention. ; Unless otherwise indicated, the wording â € œfunctionalization between 1 and 10% â € means that when the protein textile material is subjected to the barium chloride test (for example according to the method of 15 Cameron et al., as indicated above), the percentage of sulphamic acid that is bound to the fiber is less than 12%, that is, less than the maximum saturation point of the fiber. Advantageously, according to the process of the present invention, it is possible to use a raw wool fabric, in which the fibers have not been pre-selected or divided so as to be homogeneous, as is usually the case in the art. Thanks to the inhomogeneity of the fibers used and their partial reaction with the sulphamic acid, it is in fact possible to obtain a partial dyeing of the protein component, which leads to the formation of the characteristic effect of jeans. In this regard, in a preferred form, the product is made with mixed wools of different origins and / or of different lengths or diameters. ; Preferably, the application of the sulfamic acid takes place on a flat surface, for example via a padder or polisher, or even using a transfer cylinder or a printing roller, as known in the art and in any case in 30 conditions of time and concentrations such that it is possible to obtain a functionalization of the fiber between 1 and 10%, as indicated above. ; F1.G0064.12.IT.1 Dr. Guido PONTREMOLI (Register n.1397 B) ;;; 7 ;; An application that has shown this type of conditions is the following. A fabric with a composition of 100% worsted wool is impregnated in a solution of 160 g / l sulfamic acid and 160 g / l urea. An alcohol-based wetting product commonly used in the sector is added. The 5th treatment takes place at 10 m / min and the squeezing is regulated so that the fabric has a `` pick-up '' or `` charge '' after squeezing from 70 to 100% depending on the intensity of the denim effect which you want to get. After impregnation, the fabric is dried with a flat dryer (commonly called ramosa or rameuse, about 21 meters long) 10 which is adjusted to a temperature of 150-170 ° C. In this way, as the water has to evaporate, the fabric passes from an ambient temperature to about 170 ° C during the drying process. This determined, in all the cases tested, a fixing of the sulphamic acid, analyzed with the above method of 4 - 10% depending on the type of treated tissue. 15 In general, it has been noted that the main variable that determines the partial reaction of the sulfamic acid, essential for the subsequent obtaining of the denim effect, is the treatment time, which never reaches the 4 minutes indicated in the bibliography of the state of the 'art. This time can be monitored, for example, by appropriately controlling the speed 20 of the textile material inside the drying machine, as indicated in the enclosed experimental part. Therefore, in a preferred form, the present process is characterized by a drying time at the end of the impregnation with sulfamic acid, less than 4 minutes, preferably for a time of 2 minutes, even more preferably at a machine temperature of 25. drying time of about 170 ° C. If it dries for a longer time (such as in bunk branches that have distances of about 40 meters) it is necessary to increase the speed up to about 12 m / min. Therefore, in general, the steps of impregnation with sulphamic acid and of 30 drying (or â € œcuringâ €) are regulated in terms of concentration of the reagents, times and temperatures, so that at the end of said step F1.G0064.12. IT.1 Dr. Guido PONTREMOLI (Register n.1397 B) ;;; 8 ;; the fiber has a quantity of bound sulfamic acid which is less than 12%, preferably between 1 and 10%. This means that the wool fiber that forms the textile product still has free functional groups (for example - OH or - NH2) that can react with the dye, in the next 5 dyeing step to give the effect denim required. ; In this direction, dyeing can take place through the use of machinery known in the art and includes the use of a dye for wool, generally an anionic (or acid) dye or a reactive dye or a metal dye. complex, the anionic and reactive dyes 10 being particularly preferred. ; Examples of preferred reactive dyes are C.I. reactive black 5, the C.I. reactive red 195 and the C.I. reactive yellow 145. Specifically, Reactive Black 5 at the dye concentrations reported also in the following examples is able to determine the typical blue-blue color of denim 15. ; The subsequent dyeing takes place by immersing the fabric pretreated with sulfamic acid, in an acid bath, generally for formic acid, including the dye, and any dye additives, following dyeing procedures known in the art and common to the main dyeing methods 20 of the wool. According to the present invention, at the end of the dyeing the fabric has reacted only partially with the dye and therefore has the desired denim appearance. In this regard, before the final drying step, the dyed product can also be subjected to further 25 washes or soapings, as indicated for example in the enclosed experimental part. In an additional aspect, the present invention also refers to a manufactured product of protein fibers, preferably wool, obtained with the present process and having the characteristic appearance of the denim cotton fabric. In this regard, examples of preferred products are: woolen or mixed fabrics F1.G0064.12.IT.1 Dr. Guido PONTREMOLI (Register n.1397 B) ;;; 9 ;; wool, non-woven fabrics obtained with wool from the same origin or with wool mixed with other fibers. Advantageously, in fact, in accordance with the present process, it is possible to use two-dimensional products formed by one or more protein fibers of different origin, preferably 5 chosen from: in which said protein fiber product is made with mixed fibers chosen from: angora wool, merinos, cashmere, alpaca, vicuna, camel, silk and / or their blends with other fibers. In a particularly preferred form, the article is made up of mixed fibers of angora and / or merino wool and / or cashmere and / or alpaca and / or vicuna and / or camel. ; 10 In this way, by exploiting the use of raw and therefore uneven raw material, it is possible to further enhance the denim effect obtainable with this process. This process can also be applied to both carded and combed fabric, still obtaining excellent results in terms of denim effect and fastness to light, rubbing and water. Figure 1 shows a yarn-dyed cotton denim fabric known as jeans. Figure 2 shows a wool garment partially treated with sulfamic acid and dyed with the reactive black dye, according to process 20 of the present invention. The denim effect obtained is clearly visible, similar to that obtained by making a yarn-dyed cotton denim fabric, in figure 1.; The invention will now be described with the following experimental part which is not intended to be limiting, but only explanatory . ; 25; Experimental part; Example 1: procedure for obtaining a partial functionalization (1-10%) of a raw wool fabric, by reaction with sulfamic acid in the presence of urea (phase 1); 30 A fabric with a composition of 100% wool combed is impregnated in a solution of sulfamic acid 150 g / l and urea 150 g / l. An F1.G0064.12.IT.1 Dott. Guido PONTREMOLI (Register n.1397 B) ;;; 10 ;; alcohol-based wetting product is added. The treatment takes place at 10 m / min and the squeezing is regulated so that the fabric has a pick-up after squeezing about 100%. After impregnation, the fabric is dried in a twig (length of about 21 meters) which is adjusted to the temperature of 170 ° C. In this case the drying speed allowed to obtain a fiber conversion% equal to 9.5%. ;; Example 1a: dyeing of a combed wool fabric pretreated with sulfamic acid according to example 1 (phase 2); 10 Dyeing diagram with C.I. reactive black 5; Introduce the fabric into the dyeing machine (flow) and heat the dye bath to 30-35 ° C. Add formic acid in a quantity equal to 2% of fiber weight. After 2-3 minutes check that the pH is approximately = 3.; Then add the dye. ; 15 Bring the temperature from 30 ° C to 98 ° C in about 40 minutes. ; Keep at 98 ° C for 30 minutes. Cool and rinse. ; After dyeing:; Carry out a first soaping with 1 g / l of a detergent product (for example with LIVEL SUPER AM / 05 product from Guarducci) 1 g / l 20 AMMONIA solution. Maintain at 60 ° C for 5 minutes. Final rinse with water. ; If necessary, proceed with a second soaping with the same conditions as the previous one. Final rinse with water. ;; 25 Example 2: partial functionalization (1-10%) of a raw wool fabric, by reaction with sulfamic acid in the presence of urea (phase 1). ; A fabric of 100% carded wool composition is impregnated in a solution of 160 g / l sulfamic acid and 160 g / l urea. An alcohol-based wetting product 30 is added. The treatment takes place at 12 m / min and the squeezing is regulated so that the fabric has a pick-up after F1.G0064.12.IT.1 Dr. Guido PONTREMOLI (Register n.1397 B) ;;; 11 ;; squeezing about 100%. After impregnation, the fabric is dried in a bunk branch (length of about 40 meters) which is adjusted to a temperature of 160 ° C. In this case the drying speed allowed to obtain a fiber conversion% equal to 5 to 8.5%. ;; Example 2a dyeing of a carded wool fabric, pretreated with sulfamic acid according to Example 2 (phase 2). ; Dyeing diagram with C.I. reactive black 5.; 10 Departure at 30/40 ° C with the load of the fabric. ; After a few minutes the auxiliaries begin to be added in the sequence: Formic acid first to obtain starting pH 3 / 4.5; ; 2) Add sodium sulphate 10% on fiber weight; ; 3) 1/2% by weight of leveling fiber (classic of dyeing with 15 acid dyes for wool, for example Ultrafil TES / HA by Massimo Guarducci) slows down the rise and favors equalization; ; 4) introduce the dye in% based on the tone to be reproduced; 5) once the color has been introduced, the slope begins with a gradient of 1 / 1.5 ° C / min. It reaches 60 ° C and stops for 10 minutes to be sure that the color is uniformly placed between the material and the dye bath before reaching the critical temperature of 80/85 ° C where the color really begins to run out. Always with the same rising gradient, it continues to heat up to 98 ° C and is maintained for 40-45 min; after it cools down. ; 25 A first wash is carried out at 60 ° C with water and rinsing only, then the pH is adjusted to 8.5 with ammonia and (optional urea) it is heated to 80 ° C and is kept for 20 min. another wash at 60 ° C with water only as at the beginning of the soaping process. Gradients always 1.5 ° C / min. ; 30 THE MANDATORY Dr. Guido PONTREMOLI F1.G0064.12.IT.1 Dr. Guido PONTREMOLI (Register n.1397 B) 12; (Register n. 1397 B) *

Claims (3)

F1.G0064.12.IT.1 Dr. Guido PONTREMOLI (Register n.1397 B) 1 CLAIMS 1. Dyeing process of a product containing protein fibers, preferably of wool, to obtain a denim effect, said process which includes: 5 a) functionalization comprised between 1 and 10% by weight of said product by reaction of the fiber with sulfamic acid, in the presence of urea and, preferably, at least one wetting agent, and b) subsequent dyeing with anionic, reactive or metal complex dye. 2. Process according to claim 1 wherein said functionalization of step 10 a) occurs by contacting the manufactured article containing protein fibers with an aqueous solution of sulfamic acid and subsequent drying. 3. Process according to claim 2, wherein said drying takes place for about 2 minutes at 150-170 ° C, preferably at 170 ° C. 15 4. Process according to the preceding claims, in which said product is of raw wool. 5. Process according to the preceding claims, wherein said protein fiber product is made with mixed fibers selected from: angora, merinos, cashmere, alpaca, vicuna, camel, silk and / or their blends with other 20 fibers. 6. Process according to the preceding claims, wherein said protein fiber product is in the form of fabric or non-woven fabric. 7. Process according to any one of the preceding claims, in which an anionic type dye is used in the dyeing step. 25 8. Process according to any one of the preceding claims, in which a reactive type dye is used in the dyeing step. 9. Textile product containing protein fibers, preferably of wool, characterized by a denim effect obtained with the process of the preceding claims. 30 THE MANDATORY Dr. Guido PONTREMOLI F1.G0064.12.IT.1 Dr. Guido PONTREMOLI (Register n.1397 B) 2 (Register n. 1397 B)