WO2017183009A2

WO2017183009A2 - Dyeable extruded textile synthetic fibre, methods and uses thereof

Info

Publication number: WO2017183009A2
Application number: PCT/IB2017/052339
Authority: WO
Inventors: Carla Joana Dos Santos Marinho Da Silva; Nelson Manuel FEIO DURÃES; Dora Salomé CORREIA COELHO; Nelson DUARTE DA SILVA CARDOSO; Diana DA SILVA LEAL; Ana Sofia MONTEIRO SILVA
Original assignee: Centitvc- Centro De Nanotecnologia E Materiais Técnicos, Funcionais E Inteligentes
Priority date: 2016-04-22
Filing date: 2017-04-24
Publication date: 2017-10-26
Also published as: WO2017183009A3

Abstract

The present disclosure relates to an extruded textile synthetic fibre for dyeing, methods and uses thereof, namely reactive dyeing. This solution may be used in the textile industry namely for simultaneously dyeing a fabric material comprising a dyeable textile synthetic fibre of the present disclosure and natural fibres.

Description

D E S C R I P T I O N

DYEABLE EXTRUDED TEXTILE SYNTHETIC FIBRE, METHODS AND USES THEREOF

Technical field

[0001] The present disclosure relates to an extruded textile synthetic fibre for dyeing, methods and uses thereof, namely reactive dyeing.

[0002] This solution may be used in the textile industry namely for simultaneously dyeing a fabric material comprising a dyeable textile synthetic fibre of the present disclosure and natural fibres, such us cotton.

Background

[0003] Due to its typical mechanical, chemical and bacterial resistance features, as well as its low price, a thermoplastic polymer fibre, such as polypropylene (PP), is an attractive polymer when compared to other materials that are commonly used in the production of synthetic textile fibres. Nevertheless, difficulties related to the dyeing of thermoplastic polymeric fibres, in particular PP, through conventional dyeing processes have hindered the implementation and the wide use of PP in this industry. Additionally, polylactic acid (PLA), being a biodegradable polymer that can be transformed into textile fibres through melt spinning processes, has also restricted applications to this end due to limitations in its dyeing. However, PLA has interesting properties regarding its environmental impact and its resistance to UV radiation and to fire, making this polymer an attractive and promising choice for the textile industry. [0004] Presently, to overcome the problems faced in the dyeing processes of both PP and PLA, dyes are used directly in the polymeric matrix during fibre extrusion or disperse dyes are used in conventional dyeing processes instead. However, the first solution, although yielding an efficiently dyed polymer, is limited in what concerns the available colours and does not enable manufacturers to change the colours of the textile structures. On the other hand, disperse dyes do not form covalent bonds with the polymers, a clear disadvantage regarding the colour fastness of the final products.

[0005] Thus, to eradicate the above-mentioned limitations, it is necessary to use agents that ideally can be dyed with traditional reactive dyes and, at the same time, have affinity to thermoplastic polymers, namely with both polymers PP and PLA. Additionally, it is intended that these agents to not represent a significant increase in the price and do not compromise the integrity of the fibres.

[0006] The document US9534320 describes a method to fabricate fibres by wet- spinning and films manufactured from a nanofibrillated cellulose hydrogel. In the final product, the nanocellulose fibrils may be mixed with other substances, such as a polymer, antibacterial agents and/or dyes. In the solution of US9534320, the dyes are only physically entrapped on the matrix and do not establish any covalent bond with the fibre elements - a clear disadvantage towards the colour fastness (measured typically using standards ISO 105-B02:2014 and ISO 6330:2012) of the final product.

[0007] The document US9506187 discloses an advantageous process for dyeing fabrics using nanocellulose, while reducing the need for water during the dyeing process. Regardless of the dye being permanently bond to the textile material, the dyeing is achieved through the deposition of a thin film coating on the PP material.

[0008] The document US4421826 divulges a method to dye PP fibres with several dyes. However, the dyeing is achieved by treating the textile material with a dyeing aid consisting essentially of a polyurethane polymer amine salt and no claim about reactive dyeing is provided. [0009] The document KR20120131946 describes a method to dye PP with reactive dyes by twisting a single spun yarn of wool with a PP filament yarn.

[0010] The document JP2003253575 provides a method to dye fibres composed of PLA and cellulose. However, the dyeing process is based on a dye bath including a disperse dye.

[0011] The document JP2010163719 describes a method to effectively produce a dyeable composite fibre structure of PLA and cellulosic fibres. Although the method enhanced the dyeability of the fibre, it also includes several time, resources and labour consuming steps: the fibre needs to be treated with caustic soda, neutralized, washed and bleached before it can be dyed.

[0012] These facts are disclosed in order to illustrate the technical problem addressed by the present disclosure.

General Description

[0013] The present disclosure relates to a textile synthetic fibre for dyeing, methods and uses thereof, namely reactive dyeing.

[0014] This solution may be used in the textile industry namely for simultaneously dyeing a fabric material comprising a dyeable textile synthetic fibre of the present disclosure and natural fibres.

[0015] An aspect of the present disclosure relates to a dyeable extruded textile synthetic fibre obtainable by extrusion of thermoplastic polymer and cellulose mixture, comprising: thermoplastic polymer selected from a list consisting of: polypropylene, polyethylene, polylactic acid, polyvinyl alcohol, polybutylene succinate, polyurethane, polyamide, polyvinylidene fluoride, polyethylene terephthalate, polybutylene terephthalate, polyacrylate, polyvinyl acetate) and mixtures thereof; and

up to 15% (w/w) of cellulose;

wherein the thermoplastic polymer is the main component (w/w) of the fibre.

[0016] In an embodiment for better results, the synthetic fibre of the present disclosure is dyeable by a reactive dye.

[0017] In an embodiment for better results, the synthetic fibre of the present disclosure was dyed with surprisingly results by the reactive dye which is linked to the fibre, preferably the reactive dye is linked to the fibre by a covalent bond (see figures and table 3).

[0018] It was also analysed, the capabilities of both micro- and nanocellulose for the desired application were understood. Thus, it was surprisingly confirmed that the direct additivation of a thermoplastic polymer, preferably PP or PLA with micro- or nanocellulose before or after processing the fibres will enable their dyeing with reactive dyes, even when using traditional methods for cotton dyeing. The cellulose used may be in the form of filaments or in the form of crystals.

[0019] In an embodiment for better results, the thermoplastic polymer may be selected from a list consisting of polypropylene, polyethylene, polylactic acid, polyvinyl alcohol, polybutylene succinate, polyurethane, polyamide, polyvinylidene fluoride, polyethylene terephthalate, polybutylene terephthalate, polyacrylate, polyvinyl acetate), and mixtures thereof.

[0020] In an embodiment for better results, the thermoplastic polymer may be selected from a list consisting of polypropylene, polylactic acid, and mixtures thereof.

[0021] In an embodiment for better results, the synthetic fibre of the present disclosure may comprises at least 50% (w/w) of the thermoplastic polymer, preferably 50-95% (w/w) of the thermoplastic polymer, more preferably 60-85% (w/w) of the thermoplastic polymer. [0022] In an embodiment for better results, the synthetic fibre of the present disclosure may comprise between 2-12% (w/w) of cellulose, preferably between 5-10% (w/w) of cellulose.

[0023] In an embodiment for better results, the cellulose is microcellulose, nanocellulose, or mixtures thereof.

[0024] In an embodiment for better results, the cellulose is in the form of filament, crystal, or mixtures thereof.

[0025] In an embodiment for better results, the synthetic fibre of the present disclosure may comprise up to 40% (w/w) of a further polymer.

[0026] In an embodiment for better results, the further polymer is one of the following: liquid crystal polymer, polyaryletherketone, poiyetheretherketone, polyphenylene sulphide, polyamide-imide, polyether-imide, or mixture thereof.

[0027] In an embodiment for better results, the synthetic fibre of the present disclosure may comprise up to 15% (w/w) of a polymer compatibilizer agent, in particular between 0.5-10% (w/w), more in particular between 1-5 %(w/w). Preferably the compatibilizer agent is maleic anhydride or suitable copolymers.

[0028] In an embodiment for better results, the synthetic fibre of the present disclosure may further comprise an antioxidant, stabilizer, lubricant, fire retardant, blowing agent, crosslinking agent, or mixtures thereof, among others.

[0029] In an embodiment for better results, dye may be a direct dye, azoic dye, vat dye, sulfur dye, reactive dye, or mixtures thereof, among others.

[0030] In an embodiment for better results, the reactive dye is selected from a list consisting of: reactive blue, reactive orange, reactive violet, reactive red, reactive magenta, reactive yellow, reactive green, reactive turquoise blue, and mixtures thereof, among others. [0031] In an embodiment for better results, the linear mass of the fibre of the present disclosure may vary between 30 dtex - 400 dtex, preferably between 30 - 300 dtex.

[0032] In an embodiment, the present disclosure refers to a multifilament structure, namely a fabric, obtained by melt spinning extrusion. This structure may comprise synthetic and artificial thermoplastic polymers suitable to be dyeable by dyes, for improved results by reactive dyes, the thermoplastic polymer may be a PP or PLA additivated with micro and/or nanocellulose.

[0033] Spinning is a manufacturing process for producing polymeric fibres. It is a specialized form of extrusion that uses a spinneret to form multiple continuous filaments. There are many types of spinning: wet, dry, dry jet-wet, melt, gel, and electrospinning. Melt spinning is used for polymers that can be melted. The polymer solidifies by cooling after being extruded from the spinneret.

[0034] Pellets or granules of the solid polymer are fed into an extruder. The pellets are compressed, heated and melted by an extrusion screw, then fed to a spinning pump and into the spinneret.

[0035] In an embodiment, the fibres of the present disclosure may have a circular, a multilobal or a hollow cross section, and a percentage of cellulose (micro and/or nanocellulose) not higher than 15 % of the total mass of the fibre that is mainly constituted of PP, PLA or other suitable polymer. Fibres' processing will be conducted at a temperature between 160 °C and 250 °C or other suitable process temperatures, from its entrance in the extruder until its exit in the spinneret. To increase the compatibility between PP or PLA and cellulose a compatibilizer agent may also be added. In the present case, this agent is maleic anhydride, in a percentage which is not higher than 15 % (wt/wt) of the mass of PP.

[0036] In an embodiment, the linear mass of the produced fibres must be between 30 dtex and 400 dtex, preferably 30-300 dtex and they may present a monocomponent or a multicomponent structure if they are made of PP or PLA, or other synthetic polymer besides PP or PLA up to a mass percentage of 40 % (wt/wt) of the total mass of the fibre, respectively.

[0037] Another aspect of the present subject-matter relates to dyeable material or a dyed material, comprising the dyeable extruded textile synthetic fibre of the present disclosure.

[0038] In an embodiment, for better results the material may further comprise a natural fibre. Preferably, the natural fibre is cotton, silk, wool, angora, cashmere, flax, linen, or mixtures thereof.

[0039] According to the present disclosure for better results, the synthetic fibre and the natural fibre are simultaneously dyeable.

[0040] In an embodiment, for better results the synthetic fibre and the natural fibre were dyed simultaneously.

[0041] In an embodiment, for better results the material is dyed by a reactive dye.

[0042] In an embodiment, the material is a woven or non-woven textile fabric.

[0043] Another aspect of the present subject-matter relates to article comprising the fibre or the material described in the present subject matter. The article may be a clothing article, garment, wallet, bag, purse, footwear, hat, belt, home textile article or upholstery, among others.

[0044] Another aspect of the present subject-matter relates to a method for obtaining the textile synthetic fibre of the present disclosure comprising a melt spinning extrusion of the following mixture: a thermoplastic polymer selected from a list consisting of polypropylene, polyethylene, polylactic acid, polyvinyl alcohol, polybutylene succinate, polyurethane, polyamide, polyvinylidene fluoride, polyethylene terephthalate, polybutylene terephthalate, polyacrylate, poly(vinyl acetate) , and mixtures thereof;

and up to 15% (w/w) of cellulose;

wherein the thermoplastic polymer is the main component of the fibre;

preferably wherein the temperature of the extrusion is between 160- 250 °C, preferably between 180-200 °C.

Brief Description of the Drawings

[0045] The following figures provide preferred embodiments for illustrating the description and should not be seen as limiting the scope of invention.

[0046] Figure 1: Results of the reactive dyeing of sample of PLA and PLA with cellulose.

[0047] Figure 2: Results of the reactive dyeing of sample of PP and PP with cellulose.

Detailed Description

[0048] The present disclosure relates to a textile synthetic fibre for dyeing, methods and uses thereof, namely reactive dyeing.

[0049] This solution may be used in the textile industry namely for simultaneously dyeing a fabric material comprising a dyeable textile synthetic fibre of the present disclosure and natural fibres, such us cotton.

[0050] In an embodiment of the present disclosure, fibre processing conditions, dyeing and colorimetry results obtained from the CIELab system are given below. The CIELab system was developed to quantitatively define the colour of an object and it describes each colour as a unique location, numerically specified, in a three-dimensional space. The colour's position is assigned by three rectangular coordinates: lightness of the colour (L*), green-red component (a*) and blue-yellow component (b*). [0051] In an embodiment of the present disclosure, both PP and PLA fibres were processed under the conditions presented in table 1. The fibres produced in the presented conditions have linear masses between 30 dtex - 400 dtex, preferably between 30 - 300 dtex.

[0052] Table 1. It illustrates embodiments of the processing conditions of the PP and PLA fibres additivated with cellulose and maleic anhydride in different percentages.

[0053] In an embodiment of the present disclosure, to compare the effect of the additivation of the polymeric matrixes with different percentages of cellulose, two dyeing processes with two different dyes (a reactive dye and a disperse dye) were undertaken in parallel. The dyeing processes of the prepared fibres were presented in table 2. In both cases, a specific dyeing equipment that allows the control of all the necessary variables was used.

[0054] Table 2. Example of the dyeing conditions of the PP and PLA fibres additivated with cellulose and maleic anhydride.

[0055] In an embodiment of the present disclosure, the results obtained by colorimetry analysis, as well as the values obtained for the minimum reflectance (Rmin, red=530 nm and blue=600 nm), are presented in table 3. To each one of the tested fibres, both parameters ΔΕ and K/S were determined through the formulas presented below, in agreement with ASTM D2244-05 and the Kubelka-Munk theory (with red=530 nm and blue=600 nm), respectively (table 3).

ΔΕ = [(AL)²+(Aa)²+(Ab)²] ^½

K/S = (l- R_min)²/(2 Rmin)

[0056] Table 3. Results of the colorimetry analysis in CIELab scale and the values obtained for the ΔΕ e K/S parameters

*reactive dye; ** disperse dye.

[0057] In an embodiment of the present disclosure, the parameter ΔΕ represents the colour difference, and it considers the brightness, the shade and the saturation of the sample. On its hand, K/S is the colour strength of the analysed sample.

[0058] Thus, the analysis of the obtained results makes it possible to conclude that the additivation of PP or PLA with cellulose increases the values of both ΔΕ and K/S when a reactive dye is used, evidencing a relationship between the increase of the fibre colour intensity and the amount of cellulose present in the fibre.

[0059] Contrarywise, the additivation of the polymer with cellulose diminishes the intensity of the colour (K/S) of the fibre when the dyeing process is performed with a disperse dye. [0060] The term "comprising" whenever used in this document is intended to indicate the presence of stated features, integers, steps, components, but not to preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

[0061] It will be appreciated by those of ordinary skill in the art that unless otherwise indicated herein, the particular sequence of steps described is illustrative only and can be varied without departing from the disclosure. Thus, unless otherwise stated the steps described are so unordered meaning that, when possible, the steps can be performed in any convenient or desirable order.

[0062] The disclosure should not be seen in any way restricted to the embodiments described and a person with ordinary skill in the art will foresee many possibilities to modifications thereof.

[0063] The above described embodiments are combinable.

[0064] The following claims further set out particular embodiments of the disclosure.

Claims

C L A I M S

1. A dyeable extruded textile synthetic fibre obtainable by extrusion of thermoplastic polymer and cellulose mixture, comprising:

thermoplastic polymer selected from a list consisting of: polypropylene, polyethylene, polylactic acid, polyvinyl alcohol, polybutylene succinate, polyurethane, polyamide, polyvinylidene fluoride, polyethylene terephthalate, polybutylene terephthalate, polyacrylate, polyvinyl acetate) and mixtures thereof; and

up to 15% (w/w) of cellulose;

wherein the thermoplastic polymer is the main component (w/w) of the fibre.

2. The synthetic fibre according to the previous claim dyeable by a reactive dye.

3. The synthetic fibre according to the previous claim wherein the synthetic fibre was dyed by the reactive dye which is linked to the fibre.

4. The synthetic fibre according to the previous claim wherein the reactive dye is linked to the fibre by a covalent bond.

5. The synthetic fibre according to any of the previous claims wherein the thermoplastic polymer is selected from a list consisting of polypropylene, polyethylene, polylactic acid, polyvinyl alcohol, polybutylene succinate, polyurethane, polyamide, polyvinylidene fluoride, polyethylene terephthalate, polybutylene terephthalate, polyacrylate, polyvinyl acetate), and mixtures thereof.

6. The synthetic fibre according to the previous claim wherein the thermoplastic polymer is selected from a list consisting of polypropylene, polylactic acid, and mixtures thereof.

7. The synthetic fibre according to any of the previous claims comprising at least 50% (w/w) of the thermoplastic polymer.

8. The synthetic fibre according to any of the previous claims comprising 50-95% (w/w) of the thermoplastic polymer, preferably 60-85% (w/w) of the thermoplastic polymer.

9. The synthetic fibre according to any of the previous claims comprising between 2- 12% (w/w) of cellulose.

10. The synthetic fibre according to the previous claim comprising between 5-10% (w/w) of cellulose.

11. The synthetic fibre according to any of the previous claims wherein the cellulose is microcellulose, nanocellulose, or mixtures thereof.

12. The synthetic fibre according to any of the previous claims wherein the cellulose is in the form of filament, crystal, or mixtures thereof.

13. The synthetic fibre according to any of the previous claims comprising up to 40% (w/w) of a further polymer.

14. The synthetic fibre according to the previous claim wherein the further polymer is one of the following: liquid crystal polymer, polyaryletherketone, polyetheretherketone, polyphenylene sulphide, polyamide-imide, polyether-imide, or mixture thereof.

15. The synthetic fibre according to any of the previous claims further comprising up to 15% (w/w) of a polymer compatibilizer agent such as maleic anhydride or suitable copolymers, in particular between 0.5-10% (w/w), more in particular between 1-5 %(w/w).

16. The synthetic fibre according to the previous claim wherein the compatibilizer agent is maleic anhydride.

17. The synthetic fibre according to any of the previous claims further comprising an antioxidant, stabilizer, lubricant, fire retardant, blowing agent, crosslinking agent, or mixtures thereof.

18. The synthetic fibre according to any of the claims 1-17 wherein the dye is direct dye, azoic dye, vat dye, sulfur dye, reactive dye, or mixtures thereof.

19. The synthetic fibre according to any of the claims 2-18 wherein the reactive dye is selected from a list consisting of: reactive blue, reactive orange, reactive violet, reactive red, reactive magenta, reactive yellow, reactive green, reactive turquoise blue, and mixtures thereof.

20. The synthetic fibre according to any of the previous claims wherein the fibre linear mass is between 30 dtex - 400 dtex, preferably between 30 - 300 dtex.

21. A dyeable material or a dyed material, comprising the dyeable extruded textile synthetic fibre described in any of the previous claims.

22. The material according to the previous claim further comprising a natural fibre.

23. The dyeable material according to the previous claim wherein the synthetic fibre and the natural fibre are simultaneously dyeable.

24. The dyed material according to claim 22 wherein the synthetic fibre and the natural fibre were dyed simultaneously.

25. The material according to any of the claims 21-24wherein the natural fibre is cotton, silk, wool, angora, cashmere, flax, linen, or mixtures thereof.

26. The material according to any of the claims 21-24 dyed by a reactive dye.

27. The material according to any of the claims 21-26 wherein the material is a woven or non-woven textile fabric.

28. An article comprising the fibre or the material described in any of the previous claims.

29. The article according to the previous claim, wherein the article is a clothing article, garment, wallet, bag, purse, footwear, hat, belt, home textile article or upholstery.

30. A method for obtaining the textile synthetic fibre described in any of the claims 1- 19 comprising a melt spinning extrusion of the following mixture:

a thermoplastic polymer selected from a list consisting of polypropylene, polyethylene, polylactic acid, polyvinyl alcohol, polybutylene succinate, polyurethane, polyamide, polyvinylidene fluoride, polyethylene terephthalate, polybutylene terephthalate, polyacrylate, polyvinyl acetate) , and mixtures thereof;

and up to 15% (w/w) of cellulose;

wherein the thermoplastic polymer is the main component of the fibre.

31. The method according to the previous claim wherein the temperature of the extrusion is between 160- 250 °C, preferably between 180-200 °C.