EP3132084B1

EP3132084B1 - Aqueous solutions of water-soluble polymers as an adjuvant in textile pre-treatment of cotton and its blends with synthetic fibres

Info

Publication number: EP3132084B1
Application number: EP15719963.9A
Authority: EP
Inventors: Stephan Bleher; Manfred Jungen; Emrah Esder; Mas Ayu Elita Hafizah
Original assignee: Archroma IP GmbH
Current assignee: Archroma IP GmbH
Priority date: 2014-04-17
Filing date: 2015-04-17
Publication date: 2023-08-09
Anticipated expiration: 2035-04-17
Also published as: MX2016013452A; WO2015158437A3; WO2015158437A2; EP2933373C0; ES2962667T3; EP2933373A1; ES2960615T3; EP3132084A2; EP3132084C0; EP2933373B1

Description

The present invention relates to a composition, a process and methods of using aqueous solutions of polyvinylpyrrolidone (PVP) polymer in the pre-treatment of textiles comprising cellulosic fibres or a mixture of cellulosic fibres and non-cellulosic fibres.

Background of the invention

In order to arrive at textiles which are ready to be used for e.g. cloth-making, said textiles have to go through a chain of several different procedures. Each procedure provides the textiles with different properties. Examples for such procedures are pre-treatment, dyeing or finishing. The pre-treatment procedure of textiles comprising cellulosic fibers, for example cotton fibers, exists of several steps of cleaning treatments, i.e. desizing, scouring or bleaching, aiming to achieve an absorbent, hydrophilic, clean and colorless, material prepared for subsequent dyeing and finishing operations. Without thorough pre-treatment of the cellulosic fibers, neither dyeing nor finishing of the same or the respective blends with synthetic fibers gives results of high quality.
The current general pre-treatment procedure for textiles comprising cellulosic fibers by Pad Steam application requires high amounts of caustic soda (NaOH) for scouring (25-50 g/l NaOH (solid)) and/or bleaching, i.e. saponification of natural cotton waxes and fatty substances. Such high amounts of NaOH in combination with Pad Steam conditions (saturated steam of 98-100°C during 10-45 min dwelling time) are often harmful to the cellulosic fiber and can lead to reduced fabric strength, i.e. tensile and tear strength, and depolymerization of the cellulosic molecular chain, i.e. a chemically damaged fiber.
Longer steaming times with higher amounts of NaOH during alkaline scouring can often lead to crease and lay marks when the fabric is put down on a conveyor or roller belt. These crease or lay marks are visible after dyeing only and result in a faulty, non-repairable fabric appearance.
Therefore, there is a demand for a pre-treatment procedure which is less harmful to the cellulosic fiber. One approach is the so-called bio-scouring of textiles, which is a pre-treatment procedure for textiles aimed to washing and removal of natural polysaccharides and wax or polymer synthetic remains in or on cellulosic fibers using enzymes. This scouring process is preferred because it is environmentally friendly compared to conventional processes. EP 1 194 631 B for examples relates to a one-bath method for bio-scouring and dyeing of textiles using enzymes during the bio-scouring of the textiles. However, bio-scouring enzymes such as pectinolytic enzymes show only insufficient performance.
US 6,261,828 discloses a process for combined desizing and "stone washing" of dyed denim.
US 5,749,923 discloses a method and composition for chlorine free bleaching of denim textile.
US 5,711,764 discloses a decolorization and desizing process using a composition containing a reducing agent and a surfactant. A complexing agent like polyvinylpyrrolidone may be added to prevent re-deposition of degraded dye.
US 2002/115194 discloses a composition containing pectate lyase for biopreparation of cellulosic fibers.
US 5,837,010 discloses a fabric cleaning composition comprising a pectinase and PVP.
JPH09-67777 discloses an agent which comprises fine particles of a water-insoluble polymer and an enzyme wherein the enzyme is fixed to the particle.
US 3,000,830 discloses a PVP soil-suspending agent.
WO 2008/039353 A2 discloses a composition comprising pectate lyase and a non-ionic and/ or anionic surfactant.
It is therefore an object of the present invention to provide an improved process for the pre-treatment procedure for textiles comprising cellulosic fibers. It is further an object of the present invention to provide an improved composition for use in at least one step of the pre-treatment procedure.
These and other objects are achieved by the subject-matter as claimed in the claims.

Summary of the invention

In one first aspect the present disclosure relates to a process for removing impurities from textiles comprising cellulosic fibres or a mixture of cellulosic fibres and non-cellulosic fibres, wherein the process comprises at least one pre-treatment procedure, wherein the pre-treatment procedure comprises at least one step selected from desizing, scouring and bleaching, characterized in that the pre-treatment procedure comprises contacting textiles comprising cellulosic fibres or a mixture of cellulosic fibres and non-cellulosic fibres with at least polyvinylpyrrolidone (PVP) polymer in at least one step.
In one embodiment of the process according to the first aspect the PVP polymer has an average molecular weight ranging from 50,000 to 500,000 g/mol, preferably ranging from 100,000 to 400,000 g/mol, further preferred ranging from 200,000 to 300,000 g/mol.
In one embodiment of the process according to the first aspect further at least one water-soluble polymer different from PVP polymer is used and selected from the group consisting of pure or derivatised polyvinyl alcohol (PVA) homo- or copolymer; polyacrylate homo- or copolymer; polyalkyleneglycol homo- or copolymer, in particular polyethyleneglycol homo- or copolymer; modified polyalkyleneglycol homo- or copolymer, in particular modified polyethyleneglycol homo- or copolymer, in particular alkylpolyethyleneglycol homo- or copolymer, alkoxypolyethyleneglycol homo- or copolymer, acylpolyethyleneglycol homo- or copolymer; polyvinylbutyral homo- or copolymer; non-ionic or anionic modified polyesters; or non-ionic or anionic modified oligoesters; modified polystyrene, in particular low crosslinked polystyrene grafted with polyethylene glycol (TentaGelAmino Resin), or aminomethyl polystyrene; or mixtures thereof.
In one embodiment of the process according to the first aspect, the pre-treatment procedure comprises a scouring-step which comprises the addition of at least one pectinolytic enzyme to remove pectic polysaccharides from cellulosic fibers, wherein the pectinolytic enzyme is pectate lyase.
In one embodiment of the process according to the first aspect further in at least one step of the pre-treatment procedure a saccharifying enzyme to break down starch size from cellulosic fibers, e.g. an alpha-amylase is added.
In one embodiment of the process according to the first aspect the scouring step is carried out at a pH between 5 and 10, or between 7 and 8, or at 7.25.
In one embodiment of the process according to the first aspect the scouring step is carried out at a temperature between 50°C and 100°C, or between 70°C and 90°C, or at 80°C.
Further the use of polyvinylpyrrolidone polymer as an additive in the pre-treatment procedure for inhibiting crease and/or lay marks of cellulosic fibers and/or for improving liquor retention ability, whiteness, absorbency levels and/or tensile strength of cellulosic fibers is described according to a second aspect.
One object of the present invention is solved according to a third aspect by a composition of the invention comprising: a pectinolytic enzyme and polyvinylpyrrolidone whereinthe pectinolytic enzyme is a pectate lyase.
In one embodiment of the composition according to the invention the polyvinylpyrrolidone (PVP) has an average molecular weight of 50,000 to 500,000 g/mol, preferably of 100,000 to 400,000 g/mol, further preferred of 200,000 to 300,000 g/mol.
In one embodiment of the composition according to the invention the composition further comprises at least one additive selected from the group of non-ionic or anionic detergent, sequestering agent, peroxide stabilizer, or saccharifying enzyme, preferably in form of alpha-amylase, or mixtures thereof.
One object of the invention is solved according to a fourth aspect by a method according to the invention of increasing the effect of a pectinolytic enzyme, characterized by admixing said enzyme withpolyvinylpyrrolidone.
In one embodiment of the method according to the invention polyvinylpyrrolidone has an average molecular weight of 50,000 to 500,000 g/mol, preferably of 100,000 to 400,000 g/mol, further preferred of 200,000 to 300,000 g/mol
The use of a composition according to the invention in the pre-treatment of textiles comprising cellulosic fibres or a mixture of cellulosic fibres and synthetic fibres is a fifth aspect which is according to the invention.
According to the process of the first aspect crease and lay marks are reduced, preferably inhibited during further processing of the textile, in particular during Pad Steam Processing in a steamer.
According to the process of the first aspect, liquor retention ability and liquor pick-up property of the textile comprising cellulosic fibers treated according to the process of the invention is improved. Thus, the dosage of NaOH, H₂O₂ and detergent needed for scouring and/or bleaching can be reduced. This will result in a more economical processing and minimizes the danger of fiber damage since less bleaching chemicals are used.
According to the process of the first aspect, the degree of whiteness and absorbency level after bleaching, in particular after Pad Steam Processing using H₂O₂, can be improved if the textile comprising cellulosic fibers is treated according to the process according to the invention.
Further, the respective composition, method and use of the composition according to the invention have the advantage that the activity of the pectinolytic enzyme is enhanced by the water-soluble polymer, preferably by polyvinylpyrrolidone polymer and thus, the scouring ability for textiles comprising cellulosic fibers, in particular the bio-scouring ability of the process and composition according to the invention is improved.
Finally, it was shown that a combination of a water-soluble polymer and a pectinolytic enzyme provides an efficient bio-scouring step in the pre-treatment procedure for textiles comprising cellulosic fibers.

Detailed description of the invention

The process according to the first aspect of the disclosure is a pre-treatment procedure for textiles comprising cellulosic fibers or a mixture of cellulosic fibers and synthetic fibers, wherein the process comprises contacting the textile with at least polyvinylpyrrolidone polymer (PVP polymer).
The term "pre-treatment procedure" or "pre-treating" as used in the context of the present disclosure encompasses all procedures carried out to improve wettability and absorbency, dye absorption capacity, cleanness of the textile (i.e. removal of impurities), to increase whiteness, removal of tension irregularities or material irregularities resulting e.g. from a previously conducted weaving process.
Impurities contained in e.g. raw cotton from which textiles comprising cellulosic fibers can be made are, for example, natural associated impurities like hemicellulose, pectins, proteins and salts, or processing-related impurities like, for example, fatty substances, oils and waxes. It is therefore a feature of the pre-treatment procedure to remove said impurities from the cellulosic fiber by physical, chemical and biological processes in order to provide an even dye absorption capacity and to maximize the absorbency.
The pre-treatment procedure can be distinguished from subsequently following finishing procedures like dyeing, printing or equipment (e.g. equipment with fire-retardant properties) of the textile e.g. by the use of the chemicals. For example, during the dyeing or printing a dye has to be used, whereas in the pre-treatment procedure no such chemical is used. The finishing procedures aim at leaving the chemicals, e.g. the dye on or at or within the textile comprising cellulosic fibers, whereas the pre-treatment procedure aims at providing textiles comprising cellulosic fibers satisfying the requirement of subsequently following finishing steps like dyeing, printing or equipment.
The pre-treatment procedure can be conducted continuously, e.g. using the Pad Steam technology, semi-continuously, e.g. using the Cold Pad Batch technology; or discontinuously.
The pre-treatment procedure comprises at least one step selected from desizing, scouring or bleaching. The pre-treatment can comprise further steps like rinsing steps.
In one embodiment, the pre-treatment procedure consists of three steps in the mentioned order: desizing, scouring and bleaching.
The term "desizing" as used in the context of the present disclosure means the removal of sizing agents, in particular of natural sizing agents like starch or starch derivatives including protein-based starches, which are commonly employed during weaving. The removal of sizing agent can occur by degrading or solubilizing the sizing agent, in particular with the aid of at least one desizing agent. The desizing agent can be selected from saccharifying enzymes, hot water, surfactants, or other chemicals like sodium persulfate or hydrochloric acid.
In one embodiment, a saccharifying enzyme, in particular an amylase is used either alone or in combination with at least a PVP polymer.
The term "saccharifying enzyme" as used in the context of the present invention is to be understood as an enzyme which is capable of breaking down starch size on cellulosic fibers into soluble, in particular water-soluble compounds. The saccharifying enzyme can be derived from a natural source or from an alternative source including from recombinant technologies or from genetic or chemical modification. Further, the saccharifying enyzyme can be a wild type enzyme or a mutant enzyme, including functional homologues of the saccharifying enzyme. Functional homologue refers to a saccharifying enzyme that differs in the amino acid sequence or the nucleic acid sequence encoding the amino acid sequence from a wild type enzyme but is still functionally active. On the protein level a functional homologue may contain one or more mutations comprising amino acid exchanges, insertions or deletions. The saccharifying enzyme may also be chemically or enzymatically modified.
Preferably alpha-amylase is used as saccharifying enzyme.
In one embodiment, as saccharifying enzyme an alpha-amylase is used. In particular, the alpha-amylase is used in a liquid formulation. Such a liquid formulation is known under the tradenames Bactosol^® HPA liq. from Archroma or Optisize^® NEXT from Genencor^® /DuPont (CAS-No. 9000-90-2).
The desizing step can be carried out at pH value in the range between 5 to 10, or between 6 to 9, or between 7 to 8, or at 7. Further, the desizing step can be carried out at a temperature range of between 50°C to 100°C, or between 70°C to 90°C, or at 80°C.
The term "scouring" as used in the context of the present application is to be understood as the removal of further impurities, in particular of naturally occurring waxes or fatty substances or pectic polysaccharides.
The term "pectic polysaccharides" as used in the context of the present application is to be understood as polysaccharides that are rich in galacturonic acid. Pectic polysaccharides include, but are not limited to pectins, pectinates, pectates, and pectic acids.
Scouring of textiles comprising cellulosic fibers in particular encompasses the removal of fats or waxes by saponification, wherein said fats or waxes are converted into water soluble or water miscible compounds. This part of the scouring step requires the presence of at least an alkali, e.g. NaOH (caustic soda).
Scouring of textiles comprising cellulosic fibers further encompasses the removal of pectic polysaccharides. The removal of pectic polysaccharides can be conducted in the presence of at least one enzyme. If at least one enzyme is present during the scouring of textiles comprising cellulosic fibers, the term "bio-scouring" or "bio-scouring-step" is used. The at least one enzyme is in particular a pectinolytic enzyme. In one embodiment pectate lyase is used as enzyme.
In the context of the present invention, the term "pectinolytic enzyme" means a pectinolytic enzyme, preferably exhibiting lyase activity, which degrades pectic polysaccharides. The pectinolytic enzyme can be derived from a natural source or from an alternative source including from recombinant technologies or from genetic or chemical modification. Further, the pectinolytic enyzyme can be a wild type enzyme or a mutant enzyme, including functional homologues of the pectinolytic enzyme. Functional homologue refers to a pectinolytic enzyme that differs in the amino acid sequence or the nucleic acid sequence encoding the amino acid sequence from a wild type enzyme but is still functionally active. On the protein level a functional homologue may contain one or more mutations comprising amino acid exchanges, insertions or deletions. The pectinolytic enzyme may also be chemically or enzymatically modified.
One advantage (besides others already mentioned above) of using a pectinolytic enzyme during bio-scouring of textiles comprising cellulosic fibres is that the removal of other impurities, for example wax and proteins, from the cellulosic fiber of textiles is facilitated.
Pectate lyase is used as pectinolytic enzyme according to the invention. Pectate lyase belongs to the family of lyases, specifically those carbon-oxygen lyases acting on polysaccharides. The systematic name of this enzyme class is (1→4)-alpha-D-galacturonan lyase (CAS-No. 9015-75-2; EC or IUB 4.2.2.2). Pectate lyase cleaves glycosidic linkages preferentially on polygalacturonic acid.
The pectate lyase is used in form of a concentrated liquid formulation comprising the pectate lyase enzyme in pH-neutral form. Such a liquid formulation is for example known under the tradenames Bactosol^® CBS liq. from Archroma, PrimaGreen^® EcoScour liq. from Genencor^®/DuPont (CAS-No. 9015-75-2), BioScour NPL from Piscean, Addscour LLP conc. from Advanced Enzymes (CAS-No. 9032-75-1), or 601-L from Novozymes (CAS-No. 9015-75-2).
In one embodiment, the bio-scouring of textiles comprising cellulosic fibers is conducted using the composition according to the invention comprising pectate lyase and polyvinylpyrrolidone.
This has one advantage (besides others already mentioned above) that the activity of the pectate lyase is enhanced by the polyvinylpyrrolidone polymer and thus, the scouring ability for textiles comprising cellulosic fibers, in particular the bio-scouring ability of the process and composition according to the invention is improved.
The scouring of textiles comprising cellulosic fibers can further encompass the hydrolysis of proteins, dissolution of amino compounds, dissolution of mineral matter, emulsification and solubilisation of oils, removal and dispersion of dirt particles.
The scouring step can be carried out a pH value in the range between 5 to 10, or between 6 to 9, or between 7 to 8, or at 9, or at 7.25. Further, the scouring step can be carried out at a temperature range of between 50°C to 100°C, or between 70°C to 90°C, or at 80°C.
The term "bleaching" as used in the context of the present invention means the removal of coloring impurities of either natural or procedural origin from the textile comprising cellulosic fibers. The coloring impurities are usually chromophor compounds which can be degraded using bleaching agents. Thus, the degree of the whiteness level can be increased. Suitable bleaching agents are therefore of oxidizing or reducing nature, like caustic soda (NaOH) and/or H₂O₂. Further additives may be present like detergents, wetting agents, sequestering agents or the like.
In one embodiment of the disclosure an alkaline composition comprising H₂O₂ is used, either alone or in combination with at least a PVP polymer.
In one embodiment of the disclosure a mixture of NaOH and H₂O₂ is used, either alone or in combination with at least a PVP polymer.
One advantage (besides others already mentioned above) of using a combination of NaOH / H₂O₂ and at least a PVP polymer is the improvement of the degree of whiteness of the textile comprising cellulosic fibers wherein at the same time, the tensile strength of the textile comprising cellulosic fibers is also improved (compared to the tensile strength of a textile comprising cellulosic fibers which is bleached using only NaOH/H₂O₂ but no PVP polymer).
The bleaching step can be carried out a pH value in range between 9 to 12, or at 11. Further, the bleaching step can be carried out at a temperature range of between 92°C to 102°C or at 98°C.
In one embodiment of the disclosure the pre-treatment procedure comprises at least a desizing step wherein at least PVP polymer is used.
In one embodiment of the disclosure the pre-treatment procedure comprises at least a desizing step wherein at least PVP polymer is used and a saccharifying enzyme is used.
In one embodiment of the disclosure the pre-treatment procedure comprises at least a desizing step and a scouring step wherein at least PVP polymer is used in both steps.
In one embodiment of the disclosure, the pre-treatment procedure comprises at least a desizing step and a scouring step, wherein at least PVP polymer is used in both steps and a pectinolytic enzyme is used in the scouring step or at least PVP polymer is used only in the desizing step and at least a water-soluble polymer different from PVP polymer and a pectinolytic enzyme are used in the scouring step.
In one embodiment of the disclosure, the pre-treatment procedure comprises at least a desizing step and a scouring step, wherein at least PVP polymer is used in both steps and a saccharifying enzyme is used in the desizing step and a pectinolytic enzyme is used in the scouring step, or at least PVP polymer and a saccharifying enzyme are used only in the desizing step and at least a water-soluble polymer different from PVP polymer and a pectinolytic enzyme are used in the scouring step.
In one embodiment of the disclosure the pre-treatment procedure comprises at least a desizing step, a scouring step and a bleaching step, wherein at least PVP polymer is used in all three steps.
In one embodiment of the disclosure the pre-treatment procedure comprises at least a desizing step, a scouring step and a bleaching step, wherein at least PVP polymer is used in all three steps and a pectinolytic enzyme is used in the scouring step, or at least PVP polymer is used only in the desizing step and the bleaching step and at least a water-soluble polymer different from PVP polymer and a pectinolytic enzyme are used in the scouring step.
In one embodiment of the disclosure the pre-treatment procedure comprises at least a desizing step, a scouring step and a bleaching step, wherein at least PVP polymer is used in all three steps and a saccharifying enzyme is used in the desizing step and a pectinolytic enzyme is used in the scouring step.
The term "textile" as used herein refers without limitation to, fabrics, in particular woven or knitted goods.
The textile can consist essentially of cellulosic fibers. The term "textile(s) comprising cellulosic fibers" as used in the context of the present invention means that the textile can consist of cellulosic fibers and non-cellulosic fibers, wherein the non-cellulosic fibers can be synthetic fibers or non-cellulosic fibers of natural origin. The textile can comprise or consist essentially of a mixture of cellulosic fibers and synthetic fibers. Further, the textile can comprise or consist essentially of a mixture of cellulosic fibers and non-cellulosic fibers of natural origin. Further, the textile can comprise or consist essentially of a mixture of cellulosic fibers and non-cellulosic fibers of natural origin and synthetic fibers.
The term "cellulosic fiber" as used in the context of the present application refers without limitation to fibers derived from cellulose containing material, in particular from cotton, linen, jute, hemp, regenerated cellulose or mixtures thereof. Thus, cellulosic fiber means that the fibers essentially comprise or consist of cellulose-based material derived from cotton, linen, jute, hemp, regenerated cellulose or mixtures thereof.
The term "synthetic fibers" as used in the context of the present application refers to without limitation to non-cellulosic fibers which essentially comprise or consist of polyamide, polyester and/or polyurethane.
Instead of or in addition to synthetic fibers, the textile comprising cellulosic fibers can comprise further non-cellulosic fibers of natural origin like wool or silk.
The textile can comprise or consist of at least 70%, or at least 80%, or at least 90% cellulosic fibers, and wherein at most 30% (difference to 100%), or at most 20%, or at most 10% are non-cellulosic fibers, which are selected from synthetic fibers, in particular polyamide, polyester and/or polyurethane, or other non-cellulosic fibers of natural origin like wool or silk or mixtures thereof.
In one embodiment, the textile consists of 100% cellulosic fibers.
The term "contacting", respectively "contacting textiles comprising cellulosic fibers" as used in the context of the present application means that the textile comprising cellulosic fibers is at least partly, preferably essentially completely impregnated or soaked with the respective agent(s) or additive(s) required in the process according to the invention, e.g. the textile comprising cellulosic fibers is essentially completely impregnated with PVP polymer or with water or with the composition according to the invention comprising a pectinolytic enzyme and at least one water-soluble polymer, or with (a) mixture(s) with one or more compounds as described herein.
The term "polymer" as used in the context of the present application encompasses homopolymer (consisting of only one kind of monomers) as well as copolymer (consisting of at least two kinds of monomers wherein the monomers differ from each other, e.g. by having different sum formulas). The term "copolymer" as used in the context of the present application encompasses every kind of copolymer, like block copolymer or random copolymer.
The term "water-soluble polymer" as used in the context of the present application is to be understood as a polymer which is capable of being at least partly dissolved in water. The water-soluble polymer can be soluble in water at 25°C at a concentration of up to 5.0 g/l, or up to 15.0 g/l, or up to 30.0 g/l, or up to 40.0 g/l to give an optically, respectively visible clear solution. The water-soluble polymer according to the invention is polyvinylpyrrolidone.
One advantage of using polyvinylpyrrolidone in combination with pectate lyase is, that the water-soluble polymer increases the effect of the pectate lyase. This means, that the pectate lyase shows improved lyase activity, i.e. improved degradation of pectic polysaccharides. In particular the combination of PVP polymer and pectinolytic enzyme shows this advantage. Thus, a method of increasing the effect of apectate lyase, characterized by admixing said enzyme with polyvinylpyrrolidone is also one aspect of the present invention.
Suitable water-soluble polymers can be obtained e.g. under the trade name Arostit TL 0280 (polyvinylpyrrolidon, CAS-No. 9003-39-8)) from Archroma (Indonesia).
In the process according to the invention at least PVP polymer is used as water-soluble polymer. It is possible to add further water-soluble polymers selected from the group as defined above.
The term "polyvinylpyrrolidon polymer" or "PVP polymer" as used in the context of the present invention means a polymer comprising vinylpyrrolidon as monomer
The PVP polymer can have an average molecular weight of 50,000 to 500,000 g/mol, preferably of 100,000 to 400,000 g/mol, further preferred of 200,000 to 300,000 g/mol, having a residual monomer content of less than 0.01%. The amount of PVP polymer is 0.1 to 2% by weight, or 0.2 to 1.5 % by weight or 0.4 to 1% by weight, or 0.15% by weight, or 0.45% by weight, or 0.9% by weight with respect to total amount of the respective composition used in which the PVP polymer is present.
The advantage of using a PVP polymer is that crease and lay marks of cellulosic fibers during processing, in particular during Pad Steam Processing in a steamer can be inhibited. Further the PVP polymer has a favorable impact on liquor pick-up of the thus pre-treated textile comprising cellulosic fibers which has further also improved liquor retention ability. Also the degree of whiteness and absorbency level after bleaching as well as tensile strength, in particular after pad steam bleaching with H₂O₂ is improved, if PVP polymer is used.
According to the first aspect, the PVP polymer is used according to the invention as an additive in the pre-treatment procedure for inhibiting crease and lay marks of cellulosic fibers, respectively of textiles comprising cellulosic fibers and for improving liquor retention ability, whiteness, absorbency levels and tensile strength of cellulosic fibres.
The term "liquor retention ability" as used in the context of the present application refers to the ability of textiles comprising cellulosic fibers to retain more liquor and humidity during steaming on the textile, which has a favorable impact on the avoidance of crease and lay marks, since higher amounts of humidity (liquor/water) remain in or on the textile comprising cellulosic fibers after impregnation. This avoids too fast drying up of textile parts directly exposed to the steamer atmosphere and also minimizes the chemical damage of the textile after steaming. Further, the better liquor retention ability can result in an increased liquor pick up during impregnation of the textile comprising cellulosic fibers with agent(s) /additive(s) used during the process according to the invention, in particular during the pre-treatment procedure. This supports a more efficient reaction of agent(s) / additive(s) used during scouring step and/or bleaching step, which results in an improved performance in terms of whiteness and absorbency levels of the textile comprising cellulosic fibers.
The composition according to the invention comprises pectate lyase and polyvinylpyrrolidone.
Pectate lyase can be present in the composition according to the invention in form of a concentrated liquid formulation comprising the pH-neutral pectate lyase enzyme.
The composition according to the invention can be designed in form of a liquid solution or dispersion or as co-lyophilisate.
The term "co-lyophilisate" as used herein refers to a stable preparation of the composition according to the invention, obtained by rapid freezing and dehydration of the frozen composition under high vacuum.
In one embodiment, the composition according to the invention comprises pectate lyase, at least polyvinylpyrrolidone and at least one further additive.
The at least one additive can be selected from the group comprising non-ionic or anionic detergent, sequestering agent, saccharifying enzyme, peroxide stabilizer or mixtures of one or more of these additives.
The non-ionic detergent can be selected from the group comprising polyglycol ether derivatives and fatty alcohol alkoxylates or mixtures thereof. The anionic detergent can be a phosphoric acid ester. Suitable non-ionic or anionic detergents can be obtained under the trade name Hostapal XTRA liq. c. from Archroma (Thailand) (mixture of non-ionic detergents), or under the trade name Hostapal UH liq. from Archroma (China) (mixture comprising C₁₀Guebert alcohol, ethoxylated (7 EO) phosphoric ester salt), or under the trade name Hostapal DTC pa. From Archroma (Pakistan) (mixture comprising carboxylated / ethoxylated (7 EO) isotride canol), or under the trade name ALKOL D ( = Imbentin T070) from Dr. Kolb AG (CAS-No. 9043-30-5; Iso-tridecanol ethoxylated (7 EO)).
Under the term "sequestering agent" an agent is to be understood in the context of the present application which is capable of chelating earth alkalines, in particular calcium or magnesium, and/or heavy metals, in particular iron (Fe). Sequestering agents can be based on diethylenetriamine penta(methylene phosphonic acid) (DTPMP), polyacrylate and/or gluconate.
Further, a peroxide stabilizer can be present in the bleaching step, in particular if Pad Steam Bleaching is conducted. The peroxide stabilizer can be based on polyhydroxyphosphonates, polyacrylate and/or gluconate.
In one embodiment, the composition according to the invention comprises pectate lyase, at least PVP polymer, a non-ionic detergent, a sequestering agent, and an alpha-amylase.
The composition according to the invention is used in the process for removing impurities according to the invention. In particular the composition according to the invention is used in the pre-treatment procedure of textiles comprising cellulosic fibres or a mixture of cellulosic fibres and synthetic fibres. In particular the composition according to the invention is used in the scouring step of the pre-treatment procedure of textiles comprising cellulosic fibres or a mixture of cellulosic fibres and synthetic fibres.
In one embodiment of the process according to the invention, the composition comprising pectate lyase, water-soluble polymer, in particular PVP polymer, alpha amylase, sequestering agent and non-ionic detergent is being applied on a padding unit and/or roller compartment and exposed during 20 min at 80°C in a steamer (conditioned with saturated steam).

Experimental methods

The average molecular weight of the PVP polymer used herein (Arostit TL0280, CAS No. 9003-39-8) is 200.000 to 300.000 g/mol according to the GPC (Gel Permeation Chromatography) method. The residual monomer content in the PVP polymer is below 0.01% by weight.
The activity of the pectate lyase used herein was measured according a test method from DuPont Industrial Bioscience (C401-00). The principle of this test method is based on the fact that pectate lyase catalyzes the formation of double bonds in polygalacturonic acid, which can be read with an UV/VIS-Spectrophotometer at 235 nm wavelength. The double bond formation is proportional to the enzyme activity. The activity is displayed in PLU/g pectate lyase, which can be calculated out of the product between the standard equivalent curve (PLU/ml) and the sample dilution divided through the weight of sample (g).
In general, the pectate lyase is combined with a non-ionic detergent, a sequestering agent, chelating earth alkalines (Ca, Mg) and heavy metals (Fe) and, optional an alpha-amylase breaking down starch size on cotton woven fabrics.

Examples

The following chemicals were used throughout the examples.

Table 1: List of chemicals used in the Examples.

Product	Basic chemistry (main component)	Supplier	Concentration	CAS-Nr. (main component)	Dosage in recipe (g/l)
Optise ^® NEXT liq.	α-amylase	Genencor^® / DuPont	14'600 AAU/g	9000-90-2	1.0
PrimaGreen^® EcoScour liq.	Pectate lyase	Genencor^®/ DuPont	74'806 PLU/g	9015-75-2	2.0 / 5.0
Hostapal XTRA liq.c.	Mixture of non-ionic surfactants	Archroma (Thailand)	80%	mixtures	5.0
Arostit TL0280	Polyvinylpyrrolidone	Archroma (Indonesia)	30%	9003-39-8	5.0 / 15.0 / 30.0
Sirrix ANTOX liq.	DTPMP	Archroma (China)	28-32%	15827-60-8	3.0

The following compositions were used in the Examples:

Table 2: Compositions used in the Examples.

Component	Composition (units in g/l)
Component	A	B	C	D	E	F
Arostit TL0280 liq. (pure PVP polymer, Mw=200,000 g/mol)	0	0	15	15	30	30
Optise^® NEXT liq. (alpha-amylase)	1	1	1	1	1	1
Hostapal XTRA liq.c. (non-ionic detergent)	5	5	5	5	5	5
Sirrix ANTOX liq. (sequestering agent)	3	3	3	3	3	3
PrimaGreen^® EcoScour liq. (pectate lyase)	0	2	0	2	0	2

Example 1: Determination of crease (lav) mark inhibition during Pad Steam application

100% cotton woven fabric (CM50xCM50/150x80) was impregnated (liquor pick up 100%) with a composition according to Table 2 and steamed for 20 min at 80°C.

The wet crease angle recovery was directly measured after steaming. The test method followed a procedure described in AATCC 66-2003, option 2 on wet fabric, whereas a fabric sample of 40 x 15 mm was folded end-to-end, exposed for 5 min at room temperature with a 500 g weight on top and afterwards the recovery angle from a circular scale in degree (°) was evaluated. The results are shown in Table 3.

Table 3: Wet crease recovery angle according to AATCC 66-2003, option 2.

Composition	PVP [%]	Pectate lyase activity [PLU/g]	Crease angle recovery (warp)	Crease angle recovery (weft)	Crease angle recovery (warp + weft)
A	0	0	52°	57°	109°
B	0	150	53°	55°	108°
C	0.45	0	80°	92°	172°
D	0.45	150	82°	92°	174°
E	0.90	0	86°	91°	177°
F	0.90	150	85°	93°	178°

The results shown in Table 3 clearly demonstrate the positive impact of the PVP polymer on the wet crease angle recovery. All values are improved compared to compositions containing no PVP polymer. The higher the degree achieved after recovery, the less crease tendency and the less danger of crease and lay marks during steaming can be expected.

Example 2: Determination of the liquor retention ability

100% cotton woven fabric (CM50xCM50/150x80) was impregnated (liquor pick up 100%) with a composition according to Table 2 and steamed for 20 min at 80°C. After steaming the fabric was dried without rinsing and conditioned at 20°C (± 2°C) and 65% (± 2%) relative humidity for at least 4 hours.

The evaporation test followed a procedure described for evaluation of moisture management properties according to the test method from M&S (Marks & Spencer). A conditioned specimen was weighed and afterwards exposed to 1.0 ml of distilled water in a petri dish. Then the weight of the specimen was evaluated after each 5 min up to 30 min time. The remaining water in the fabric was calculated in % with regard to the initial weight (at 0 min) of the fabric.

Table 4: Liquor retention ability according to M&S (Marks & Spencer).

Composition	Time	PVP	Pectate lyase activity	Remaining water
	[min]	[%]	[PLU/g]	[%]
B	0	0	150	100
D		0.45	150	100
C		0.45	0	100
B	5	0	150	98.7
D		0.45	150	98.6
C		0.45	0	98.6
B	10	0	150	96.1
D		0.45	150	96.3
C		0.45	0	96.2
B	15	0	150	94.6
D		0.45	150	94.6
C		0.45	0	94.7
B	20	0	150	92.4
D		0.45	150	93
C		0.45	0	93.1
B	25	0	150	88.1
D		0.45	150	89.1
C		0.45	0	89
B	30	0	150	85.5
D	30	0.45	150	87.3
C		0.45	0	87.2

The results shown in Table 4 demonstrate an improvement in liquor retention in particular after dwelling times > 20 min. The more water remains after a certain time in the fabric (i.e. the less weight difference compared to the initial weight), the better the liquor retention ability and the better the effects described.
The ability to retain more liquor and humidity during steaming on the textile also has a favorable impact on avoidance of crease and lay marks, since higher amounts of humidity (liquor/water) remain on the textile after impregnation. This avoids too fast drying up of fabric parts directly exposed to the steamer atmosphere and also minimizes the chemical damage of the fabric after steaming.
Higher liquor retention ability also results in an increased liquor pick up during impregnation. This supports a more efficient reaction of (scouring and bleaching) chemicals with the fiber. Thus, higher liquor retention ability leads to an improved performance in terms of the whiteness and absorbency levels achieved after scouring and bleaching.

Example 3: PVP in continuous pre-treatment: Performance improvement during alkaline scouring and H ₂ O ₂ -bleaching (Pad Steam).

The performance of the process according to the invention, respectively the performance of the composition according to the invention used in the bio-scouring step can be determined using a Ruthenium Red dyestuff solution applied to the textile after treating the same with the composition according to the invention, which indicates the amount of pectin remaining on the cotton fiber. The lighter the red color after the dyeing process, the less pectin remained on the cotton fiber and, thus, the better are the scouring abilities, in particular the bio-scouring abilities of the composition according to the invention, respectively the process according to the invention.
100% cotton woven fabric (CM80/2xCM80/2/160x72) was impregnated (liquor pick up 100%) with a composition according to Table 2, steamed for 20 min at 80°C and 98°C, respectively, and afterwards washed off with hot, warm and cold demineralized water.

The degree of whiteness (C.I.E.) was measured using a Datacolor Spectrophotometer (650).

Table 5: Whiteness improvement during Pad Steam processing (3 step treatment).

Process	Composition	PVP [%]	Enzyme activity [AAU/g] [PLU/g]	C.I.E.	Yellow Index (DIN 6167)	Ruthenium Red [%]
Grey fabric (untreated)		-	0	-11.2	30.9	100
Desizing (pick up 100%, 20 min at 80°C)	A	0	0	8.7	25.4	76.2
Desizing (pick up 100%, 20 min at 80°C)	C	0.45	150	11.1	24.7	36.6
Scouring (pH 9.0, pick up 100%, 20 min at 80°C)	A	0	0	8.3	25.5	32
Scouring (pH 9.0, pick up 100%, 20 min at 80°C)	D	0.45	150	11.6	24.4	31.2
Bleaching (pH 11, 9.5 g/l H₂O₂ (100%), pick up	A	0	0	56.3	11.5	29.5
Bleaching (pH 11, 9.5 g/l H₂O₂ (100%), pick up	C	0.45	0	65.8	8.8	29

Process	Composition	PVP [%]	Enzyme activity [AAU/g]	C.I.E.	Yellow Index (DIN 6167)	Ruthenium Red [%]
Process	Composition	PVP [%]	[PLU/g]	C.I.E.	Yellow Index (DIN 6167)	Ruthenium Red [%]
100%, 20 min at 98°C)

The absorbency level was measured according a modified AATCC test method (197-2012-Vertical Wicking of Textiles, Clariant Internal Test Method TM 7302) or the drop test method according to TEGEWA: a drop of colored water was placed on the surface of the fabric and the time was evaluated (in sec.), until the drop had been completely absorbed up from the fabric and b) according the wicking height method, whereas a sufficient amount of dye solution was filled into a Petri dish, minimal height 15 mm. Then the textile test stripes were suspended in the dye solution so that the bottom end just penetrated the surface of the solution. The stripes were dipped for approximate 2-3 mm. The time was evaluated with a stop watch and after 5 min, the stripes were removed and dried between layers of absorbent paper. The height was evaluated in mm.

Table 6: Absorbency improvement during Pad Steam processing (3 step treatment).

Process	Composition	PVP [%]	Enzyme activity [AAU/G]	Wicking height [mm]	Drop test [sec]
Process	Composition	PVP [%]	[PLU/g]	Wicking height [mm]	Drop test [sec]
Grey fabric (untreated)		0	0	0	>60
Desizing (pick up 100%, 20 min at 80°C)	A	0	0	1	>60
Desizing (pick up 100%, 20 min at 80°C)	C	0.45	150	5	>60
Scouring (pH 9.0, pick up 100%, 20 min at 80°C)	A	0	0	12	26
Scouring (pH 9.0, pick up 100%, 20 min at 80°C)	D	0.45	150	18	8
Bleaching (pH 11, 9.5 g/l H₂O₂ (100%), pick up 100%, 20 min at 98°C)	A	0	0	22	2
	C	0.45	0	29	1

Table 5 and Table 6 show that addition of PVP polymer leads to better performances in terms of whiteness and absorbency levels. The higher the wicking height and the shorter the time of the drop test, the better the absorbency of the fabric.

Tensile strength was determined according to ISO 13934-1. A test specimen is extended at a constant rate until it ruptures. The maximum force at rupture is recorded. The higher the value (force) or the more close the value compared to the untreated, grey fabric, the better the performance.

Table 7: Tensile strength improvement during Pad Steam processing (determination after scouring & bleaching).

Process	Composition	PVP [%]	Pectate lyase activity [PLU/g]	Tensile strength [cN] (warp direction only)
Grey fabric		-	-	1074.3
Scouring (pH 9.0, pick up 100%, 20 min at 80°C)	D	0.45	150	1050.5
Bleaching (pH 11, 9.5 g/l H₂O₂ (100%), pick up 100%, 20 min at 98°C)	D	0.45	0	1020.8

Process		Composition	PVP [%]	Pectate lyase activity [PLU/g]	Tensile strength [cN] (warp direction only)
Reference process (50.0 g/l NaOH (solid), 9.5 g/l H₂O₂ (100%))
	- Scouring		-	-	975.8
	- bleaching		-	-	922.5

Table 7 demonstrates that the tensile strength of the textile is clearly improved in the presence of PVP compared to the reference processes.

Example 4: Determining the bio-scouring effect in continuous Pad Steam application on 100% cotton woven fabric

100% cotton woven fabric (CM80/2xCM80/2/160x72) was impregnated (liquor pick up 100%) with the respective composition, steamed for 20 min at 80°C at pH 7.0 and afterwards washed off with hot, warm and cold demineralized water.

The dryed textile samples were then dyed in a Launder-O-Meter (LOM) at liquor ratio 20:1 at 50°C for 30 min in 250 ml of a 0.05% w/w Ruthenium Red staining solution in phosphate buffer at pH 6.0. After dyeing, the samples were washed off with warm demineralized water, dried and then, color strength (%) and color difference (dE*) were measured with Datacolor Spectrophotometer 650.

Table 8: Continuous bio-scouring effects.

Composition	Dosage [g/l]	Pectate lyase activity [PLU/g]	PVP [%]	Ruthenium Red [%]	dE*
Grey fabric (untreated)	-	-	-	100	47.1
100% H₂O	-	0	0	76.1	43.6
10% PrimaGreen^® EcoScour liq., 90 % H₂O	2	150	0	55	38.5
15% PrimaGreen^® EcoScour liq., 35% Arostit TL0280, 50% H₂O	20	224	0.21	50.8	38.2
15% PrimaGreen^® EcoScour liq., 35% Arostit TL0280, 50% H₂O	35	393	0.367	45.7	34.5
10% PrimaGreen^® EcoScour liq., 40% Arostit TL0280, 50% H₂O	20	150	0.24	52.1	36.6
10% PrimaGreen^® EcoScour liq., 40% Arostit TL0280, 50% H₂O	35	262	0.42	50.1	36.6
5% PrimaGreen^® EcoScour liq., 45% Arostit TL0280, 50% H₂O	20	75	0.27	57.6	41.2
5% PrimaGreen^® EcoScour liq., 45% Arostit TL0280, 50% H₂O	35	131	0.472	52.5	38.6
2.5% PrimaGreen^® EcoScour liq., 47.5% Arostit TL0280, 50% H₂O	20	37	0.285	65.9	43.1
	35	65	0.499	62.1	42.2
16% PrimaGreen^® EcoScour liq., 64% Arostit TL0280, 20% H₂O	20	239	0.384	55.8	39.9
16% PrimaGreen^® EcoScour liq., 64% Arostit TL0280, 20% H₂O	35	419	0.672	50.9	38.7

As shown in Table 8 pectate lyase in combination with PVP polymer leads to a reduced color strength of Ruthenium Red and minimizes color difference compared to the untreated, grey fabric, demonstrating the improved bio-scouring effect in the continuous pre-treatment. The lower the values for the color strength (%) and color difference (dE*) compared to the untreated, grey material, the better the bio-scouring effect.

Claims

Composition comprising
i. a pectinolytic enzyme and

ii. polyvinylpyrrolidone
wherein the pectinolytic enzyme is a pectate lyase.
Composition according to claim 1, wherein the polyvinylpyrrolidone (PVP) has an average molecular weight of 50,000 - 500,000 g/mol, preferably of 100,000 to 400,000g/mol, further preferred of 200,000 to 300,000 g/mol.
Composition according to any of claims 1 or 2, further comprising at least one additive selected from the group of non-ionic or anionic detergent, sequestering agent, peroxide stabilizer, or saccharifying enzyme, preferably in form of alpha-amylase, or mixtures thereof.
Method of increasing the effect of pectate lyase, characterized by admixing said enzyme with polyvinylpyrrolidone,
wherein the polyvinylpyrrolidone (PVP) has an average molecular weight of 50,000 to 500,000 g/mol, preferably of 100,000 to 400,000g/mol, further preferred of 200,000 to 300,000 g/mol.
Use of a composition according to any one of claims 1 to 3 in the pre-treatment of textiles comprising cellulosic fibres or a mixture of cellulosic fibres and synthetic fibres.