Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/0004—General aspects of dyeing
  • D06P1/0012—Effecting dyeing to obtain luminescent or phosphorescent dyeings
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
  • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
  • D06P1/5292—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds containing Si-atoms

Definitions

• This invention relates to a dyeing method for fibres, yarns, fabrics and garments, in particular for protein-based natural fibres, to obtain fibres, yarns, fabrics and garments with fluorescent properties.
• the invention relates to a cold dyeing method characterised by temperatures of below 60 °C with an overall treatment time of less than two hours and which does not use strong mineral acids.
• the method according to the invention directly uses fluorescent dyes, preferably acid dyes belonging to group I, either in their soluble form or in the form of fluorescent hybrid pigments, the latter comprising an inorganic carrier and an organic component belonging to fluorescent dyes, preferably acid dyes belonging to group I.
• the method according to the invention uses previously hydrolysed organo-functionalised siloxanes as a binding agent to covalently fix fluorescent dyes or fluorescent pigments on fibres, yarns, fabrics and garments, with the aim of producing textile products with special fluorescent characteristics and high visibility, distinct light stability and excellent wet solidity.
• the reactivity is guaranteed by a rapid diffusion of the acid substances, with a low molecular weight, towards the carboxylic groups of the fibre which are protonated in this way.
• a high level of protonation characterised by the presence of functional groups such as COOH, and taking advantage of the amphoteric nature of the protein fibres, several reactive points are obtained, characterised by the formation of NH3 + type groups.
• This cationic form interacts with the ionic dye (X-), dissolved in the aqueous bath, thus forming an anionic complex with strong electrostatic interaction between the protein-based fibre and the colour.
• the times and temperatures of the various dyeing baths vary according to the type of dye chosen.
• the dyeing is carried out with fluorescent colours belonging to the group I (acids) achieving results which are substantially satisfactory for the different levels of solidity required.
• Table 1 shows the solidity values of the most common acid fluorescent colours (Group I) currently available on the market.
• the dyeing of protein fibres can be performed with different classes of dyes.
• Each class of dyes has its own particular operating conditions.
• the three classes of acids for wool force dyers to have for each class their own chemical auxiliaries (acids and/or salts), dyestuffs and dyeing profiles with a high expenditure of thermal energy over time.
• keeping the material at high temperatures for a long time also leads to a deterioration of the physical-mechanical qualities of the fibres.
• the technical problem raised and solved by the invention is that of providing an innovative method for dyeing textile yarns which allows the above-mentioned drawbacks of the prior art to be overcome.
• the invention aims to provide a bland dyeing method, unique for all types of protein fibres, which allows fluorescent pigments, fluorescent dyes and fluorescent brightening to be covalently bound in clothing textiles and ensuring a distinct light solidity and excellent washing solidity.
• the method according to the invention achieves the following benefits:
• the invention relates to an innovative dyeing method, wherein a dyed and/or raw natural fibre yarn is dyed with fluorescent dyes or with a fluorescent pigment comprising fluorescent dyes.
• This fluorescent pigment is a 2D nanostructured pigment with optimised optical activity.
• 'fluorescent pigment' when used in the invention, it means a hybrid pigment with optimised optical activity consisting of an organic fluorescent molecule, for example, an acid fluorescent dye of group I, intercalated or absorbed in an inorganic system, in which the organic fluorescent molecule, in its anionic form, has been intercalated and/or absorbed in the inorganic system by direct reactions or by means of intermediaries.
• Said inorganic system is a lamellar solid, preferably of the layered double hydroxides type - LDH, more specifically belonging to the hydrotalcites family.
• the dyeing method according to the invention makes it possible to obtain a nano-coating or surface coating of fluorescent dye or fluorescent pigment on the fibre in a single step and under bland conditions (below 60 °C), through the formation of a covalent bond between the fibre and the fluorescent dye or between the fibre and the fluorescent pigment, regardless of the type of fibre or textile clothing product. This allows the fluorescence characteristics to be transferred to the natural fibre.
• the result of the dyeing method according to the invention is a fluorescent textile clothing product with high visibility, high wet solidity and distinct light solidity.
• the method according to the invention is suitable for dyeing fibres, yarns, fabrics and garments made of protein-based natural fibres, such as wool, cashmere, mohair, angora, silk and related blends of the above- mentioned fibres.
• the aim of the invention is to provide a unique and universal dyeing method which groups together all the dyeing classes currently existing for natural protein fibres into a single operational method.
• the dyeing method according to the invention uses a fluorescent dye or a fluorescent pigment which, when fixed to a textile product, transfers the above-mentioned fluorescent activity to the textile substrate, providing a fluorescent textile product which preserves the fluorescent characteristics of the dye or the starter pigment and is characterised by an access colour with high visibility and homogeneity.
• the invention therefore proposes an innovative dyeing procedure based on the formation of covalent bonds between a fluorescent dye or the inorganic part of a fluorescent pigment and the functional groups of a natural textile substrate, such as primary and secondary amine, hydroxyl and carboxylic groups.
• the covalent bond is preferably formed by the reaction between reactive organo-functional siloxane agents (adhesion promoters) and natural fibres such as wool, silk, mohair, cashmere and their mixtures and fluorescent dyes or pigments in water under mild thermal conditions.
• the mild heat treatment according to the invention promotes the formation of a rapid condensation reaction between the hydroxyl groups of the inorganic part or the reactive groups of the fluorescent dye and the functional groups present in the natural fibres (hydroxyl, carboxyl and primary and secondary amine), mediated by the presence of an additive which promotes adhesion.
• the various organic functions (amine, epoxy, alkoxide) contained in the adhesion promoter additive are able to react in the medium, producing by-products such as diols and alcohols, and covalently bind the textile fibres with the fluorescent pigments or dyes used.
• the dyed product thus obtained is highly resistant to further hydrolysis and washing reactions.
• the method according to the invention is advantageously innovative in terms of the method and stage of application of the organo- functioning siloxanes in the presence of fluorescent dyes or fluorescent pigments.
• the dyeing method according to the invention makes it possible to obtain a textile product with characteristics of high visibility and fluorescence when irradiated with UV light and high thermal, photochemical and washing stability.
• the dyeing method according to the invention advantageously allows excellent light solidity and wet solidity values to be obtained, which comply with the Chinese standard GB 18401 for products for adults.
• the solidity values obtained by applying the method according to the invention to a wool yarn are shown in Table 2. Table 2
• the dyeing method according to the invention also makes it possible to preserve the noble characteristics of the natural fibres, such as softness and brilliance, as the dyeing operations are carried out at temperatures not exceeding 60 °C and in less than 2 hours.
• There are no other additives/reagents such as sulphuric acid, acetic acid, equalising agent, formic acid, ammonium acetate, ammonium sulphate and there is a reduced number of operations, which are also fully compatible with current industrial procedures for dyeing skeins and/or spools.
• the temperature ramp is fast and fully compatible with the normal operations of adding of the yarn to be treated, dispersing the pigment or dye and adding the siloxane binding agent, all in a time not exceeding 15 - 25 mins.
• a further advantage of the dyeing method according to the invention is that it does not discriminate the type of fluorescent pigment, so the same procedure can be applied for pigments based on lamellar solids type LDH and Zr phosphates.
• FIG. 1 shows a known dyeing process of wool in a strongly acidic bath
• FIG. 2 shows a known dyeing process of wool in a weakly acidic bath
• FIG. 3 shows a known dyeing process of wool in a neutral bath
• FIG. 4 shows a schematic view of an application example of the tracer dyeing process according to the invention.
• A immersion of the wool yarn in purified water and addition of the siloxane agent;
• B addition of the fluorescent pigment or colour.
• the specific object of the invention is therefore a dyeing method for colouring or dyeing a protein-based natural fibre by means of a fluorescent dye or a fluorescent pigment, comprising the steps of: a) preparing a natural fibre in a dyeing tank with water; b) adding a siloxane agent in said tank; c) dispersing a liquid colouring solution comprising a fluorescent dye or fluorescent pigment in said tank; d) heating said dyeing tank comprising said natural fibre, said siloxane agent and said colouring solution at a temperature comprised between 50 °C and 70 °C, preferably at 60 °C; e) keeping said temperature constant for a time comprised between 1 and 3 hours.
• the fluorescent pigment is a pigment, comprising:
• an organic fluorescent filler configured to be intercalated or absorbed between the lamellae of said inorganic matrix.
• the organo-functionalised siloxane-based binding agent for example previously hydrolysed, is used to create a coating to the support, meaning yarn, fibre, fabric or garment.
• the siloxanes can be added to the dyeing bath even before the dyes.
• the siloxane When, on the other hand, a pigment is used which is insoluble in the dyeing bath because it is a solid material, the siloxane must be added to the dyeing bath before the pigment is inserted so that it can be fixed on fibres, yarns, fabrics and garments.
• the siloxane agent is added in said tank in a percentage by weight less than or equal to 10% by weight of the fibre, preferably between 0.1% and 5% when a fluorescent dye is used and between 5% and 10% when a fluorescent pigment is used.
• the siloxane agent is chosen, for example, from amine / epoxy / octyl / methoxy / ethoxy functionalised hydrolysed siloxane agents such as Dynasylan Hydrosil 1153, Dynasylan Hydrosil 2627, Dynasylan Hydrosil 2926, Dynasylan Hydrosil 2776, Dynasylan Hydrosil 2909 (Evonik commercial products).
• the liquid colouring solution comprises a mixture of purified water and fluorescent dye or purified water and fluorescent pigment wherein the quantity of fluorescent dye or fluorescent pigment with respect to the amount of water is between 5-15 grams of pigment per litre of water.
• Preferred embodiments comprise a liquid colouring solution with a percentage by weight of fluorescent dye or fluorescent pigment of between 0.1% and 5%, with respect to the weight of the natural fibre, preferably approximately 2% fluorescent pigment or approximately 0.25% fluorescent dye.
• the dyeing process according to the invention comprises the immersion of the fibres, yarns, fabrics and/or garments in the dyeing bath.
• the dyeing bath comprising said fibre, said siloxane agent and said colouring solution is then homogenised, in particular for a time comprised between 10 and 20 minutes for the phase relating to yarn plus siloxane agent homogenisation. Subsequently, the dyeing bath is brought to a temperature of 60 °C for a period of time between 1 and 3 hours, preferably 2 hours. Finally, the overpressure dyeing bath is drained and the fibre is rinsed three times.
• the result is a fibre, yarn, fabric and/or garment with the fluorescent dye or fluorescent pigment covalently bonded and optically active to UV radiation.
• the natural fibre preferably in a configuration wound on a spool, or reel, or skein, is placed in water, with a ratio between said fibre and said water of between 1 mg/ml and 20 mg/ml.
• the pH is advantageously kept equal to the isoelectric point of the natural fibre, for example at a value of approximately 4.7.
• fluorescent pigments are used wherein the inorganic matrix comprises components belonging to the hydrocyte group, in particular layered double hydroxides (LDH), optionally MgAI and ZnAI, or lamellar solids such as zirconium phosphates.
• LDH layered double hydroxides
• MgAI and ZnAI optionally MgAI and ZnAI
• lamellar solids such as zirconium phosphates.
• the organic molecule of the fluorescent pigment comprises: fluorescent dyes such as Sodium 2-[7-(diethylamine)-2-oxo- 2H-chromen-3-yl]-5-sulfamoyl-2,3-dihydro-1 ,3-benzoxazole-2-sulfonate (CAS 93859-32-6) (Yellow Fluo Cromacid 8GX) and Sulforhodamine B sodium salt (CAS 3520-42-1 )(Red Fluo Cromacid B), optical brighteners or bleaches such as Fluorescent Brightener, optionally Fluorescent Brightener 351 , or Group I acid dyes, stilbene dyes, rhodamine dyes and dyes based on benzoxazole derivatives.
• fluorescent dyes such as Sodium 2-[7-(diethylamine)-2-oxo- 2H-chromen-3-yl]-5-sulfamoyl-2,3-dihydro-1 ,3-benzo
• the fluorescent pigment may be composed of an inorganic component of the lamellar solids type belonging to the family of layered double hydroxides (LDH) known as hydrotalcite, with the formula [M2+1 -xM3+x(0H)2][An-]x/n-zH20 (3:1 Mg/AI ratio, co-intercalated with counterion nitrate and/or carbonate and/or water molecules), absorbed with the organic molecule belonging to the family of acid fluorescent dyes of the group I 4 Sulforhodamine B sodium salt (CAS 3520-42-1 )(Red Fluo Cromacid B).
• LDH layered double hydroxides
• the fluorescent pigment may be composed of an inorganic component of the lamellar solids type belonging to the family of layered double hydroxides (LDH) known as hydrotalcite, with the formula [M2+1 -xM3+x(0H)2][An-]x/n-zH20 (3:1 Mg/AI ratio, co-intercalated with counterion nitrate and/or carbonate and/or water molecules), absorbed with the organic molecule belonging to the family of the acid fluorescent dyes (benzoxazole derivative) Sodium 2-[7-(diethylamino)-2-oxo-2H- chromen-3-yl]-5-sulfamoyl-2,3-dihydro-1 ,3-benzoxazole-2-sulfonate (CAS 93859-32-6) (Yellow Fluo Cromacid 8GX).
• LDH layered double hydroxides
• the clothing textile product has high visibility, is characterised by a fluorescence when irradiated with UV light and has distinct solidity to light and excellent solidity to wet treatments.
• a fluorescent dye is used chosen from fluorescent dyes such as Sodium 2-[7-(diethylamine)-2-oxo-2H-chromen-3-yl]-5-sulfamoyl-2,3- dihydro-1 ,3-benzoxazole-2-sulfonate (CAS 93859-32-6) (Yellow Fluo Cromacid 8GX) and Sulforhodamine B sodium salt (CAS 3520-42-1 )(Red Fluo Cromacid B), optical brighteners or bleaches such as Fluorescent Brightener, optionally Fluorescent Brightener 351, or Group I acid dyes, stilbene dyes, rhodamine dyes and dyes based on benzoxazole derivatives.
• fluorescent dyes such as Sodium 2-[7-(diethylamine)-2-oxo-2H-chromen-3-yl]-5-sulfamoyl-2,3- dihydro-1 ,3-benzoxazole-2-sulf
• the dyeing method according to the invention increases the compatibility between the textile product and the fluorescent dye or fluorescent pigment, as it allows the formation of a thermally stable covalent bond, formed by condensation reactions between the hydroxyl groups (-OFI) of the inorganic part or the reactive groups of the fluorescent dye with the functional groups present on the natural fibres (hydroxylic, carboxylic, primary amine and secondary amine), mediated by the presence of an adhesion promoting additive, such as siloxane agents with reactive functions.
• an adhesion promoter based on siloxane oligomers reactive in aqueous medium, activated at a temperature below 60 °C is used.
• the dyeing method according to the invention there are no other additives/reagents such as sulphuric acid, acetic acid, equalising agent, formic acid, ammonium acetate, ammonium sulphate and there is a reduced number of operations, which are also fully compatible with current industrial procedures for dyeing skeins and/or spools.
• additives/reagents such as sulphuric acid, acetic acid, equalising agent, formic acid, ammonium acetate, ammonium sulphate and there is a reduced number of operations, which are also fully compatible with current industrial procedures for dyeing skeins and/or spools.
• the temperature ramp is fast and fully compatible with the normal operations of adding the yarn to be treated, dispersing the pigment or dye and adding the siloxane bonding agent, all in a time not exceeding 15 - 25 mins.
• Figure 4 which shows a diagram of the method according to the invention in which a wool yarn is used and a siloxane bonding agent Flydrosyl 2926 of between 5 and 10% by weight with respect to the weight of the fibre and a fluorescent acid dye or a smart pigment of between 0.25 and 2% by weight with respect to the weight of the fibre
• the maximum dyeing temperature applied in the method according to the invention represents the minimum temperature used in the traditional methods shown in Figures 1 , 2, and 3.
• the invention also relates to a textile product made of protein- based natural fibres with fluorescent properties, comprising a fluorescent dye or fluorescent pigment as defined above, wherein said fluorescent dye or fluorescent pigment is bound to the protein-based natural fibre by a covalent bond.
• a garment textile product having fluorescent properties dyed with a dye or organic component belonging to the family of acid fluorescent dyes of group 1 , preferably Sodium 2-[7-(diethylamino)- 2-oxo-2H-chromen-3-yl]-5-sulfamoyl-2,3-dihydro-1 ,3-benzoxazole-2- sulfonate (CAS 93859-32-6) (Yellow Fluo Cromacid 8GX) or - Sulforhodamine B sodium salt (CAS 3520-42-1 )(Red Fluo Cromacid B), covalently bound to the fibre by the dyeing method according to the invention, which is a highly visible garment textile product, characterised by a fluorescence when irradiated under UV light and excellent solidity to wet treatments.
• a dye or organic component belonging to the family of acid fluorescent dyes of group 1 preferably Sodium 2-[7-(diethylamino)- 2-oxo-2H-chromen-3-y
• the invention relates to a garment textile product having fluorescent properties, dyed with an optical brightener or organic component belonging to the family of fluorescent optical brighteners preferably Fluorescent Brighter 351 , covalently bonded to the fibre by the dyeing method according to the invention, which results in a garment textile product characterised by a fluorescence when irradiated under UV light and of distinct light solidity and excellent solidity to wet treatments.
• EXAMPLE 1 Example of the dyeing method according to the invention.
• the method for dyeing yarns according to the invention described below is a spool or skein dyeing process compatible with an industrial process (Process A) and comprises the following steps:
• siloxane agent directly to the bath, in a quantity of up to 10% with respect to the weight of the fibre; preferably between 0.1 and 5% by weight for the acid dye and between 5 - 10% by weight for the fluorescent pigment.
• step 5 Dosing the solution/dispersion made in step 5 in the tank containing the yarn and the siloxane agent;
• EXAMPLE 2 Method of dyeing, according to present invention, natural protein fibres (wool) with fluorescent pigments LDH_Red_1 and LDH_ Yellow_ 1.
• the fluorescent pigments used consist, respectively, of the organic molecules Sulforhodamine B sodium salt (CAS 3520-42-1) (Fluo Red Cromacid B - Fuchsia) and Sodium 2-[7-(diethylamino)-2-oxo-2H-chromen-3-yl]-5- sulfamoyl-2,3-dihydro-1 ,3-benzoxazole-2-sulfonate (CAS 93859-32-6) (Fluo Yellow Cromacid 8GX). Both dyes have been absorbed in a precursor hydrotalcite type Aluminium Magnesium Hydroxide Nitrate- LDH_N03 (CAS 148884-57-5).
• the resulting pigments were applied to wool fibres according to the method described in Example 1.
• EXAMPLE 3 Method of dyeing, according to the invention, for natural protein fibres (wool) with Red Fluo Cromacid B and Yellow Fluo Cromacid 8GX.
• the wool protein fibre was dyed, according to the method shown in Example 1 , with the fluorescent dyes Sulforhodamine B sodium salt (CAS 3520-42-1 )(Fluo Red Cromacid B) and Sodium 2-[7-(diethylamino)- 2-oxo-2H-chromen-3-yl]-5-sulfamoyl-2,3-dihydro-1 ,3-benzoxazole-2- sulfonate (CAS 93859-32-6) (Fluo Yellow Cromacid 8GX), respectively.
• Sulforhodamine B sodium salt CAS 3520-42-1
• Sodium 2-[7-(diethylamino)- 2-oxo-2H-chromen-3-yl]-5-sulfamoyl-2,3-dihydro-1 ,3-benzoxazole-2- sulfonate CAS 93859-32-6) (Fluo Yellow Cromacid 8GX), respectively.
• EXAMPLE 4 Method of dyeing, according to the invention, natural protein fibres (wool) with Fluorescent Brightener 351 (CAS 27344-41-8).
• the wool protein fibre was dyed with Fluorescent Brightener 351 (CAS 27344-41-8).

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Coloring (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=71170699

Family Applications (1)

Country Status (2)

Family Cites Families (2)

• 2020
  • 2020-04-30 WO PCT/IT2020/000038 patent/WO2021220312A1/en unknown
  • 2020-04-30 EP EP20735033.1A patent/EP4143379A1/de active Pending

Also Published As

Similar Documents

Legal Events