Textiles, new copolymers / method for imparting antibacterial properties to textiles

Abstract

To provide an improved method for providing an anti-microbial and an anti-pilling effect to textiles and for improving dye uptake to textiles.SOLUTION: The method comprises treating a textile with an aqueous solution comprising a) and b) in the following: a) at least one copolymer made of the general formulas (I) and (II) in the figure; and b) at least one aliphatic or cycloaliphatic diisocyanate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for imparting antibacterial and antipilling effects to textiles and a method for improving dye uptake into textiles. The present invention also relates to novel copolymers and novel textiles for use in the methods of the present invention. [Background technology]

[0002] Antimicrobial, and in particular antibacterial, textiles are known in the art and are typically prepared by applying an antibacterial substance to the textile or yarn, which must, of course, be non-toxic and non-allergenic to human skin.

[0003] Currently, antibacterial agents are generally selected from quaternary ammonium compounds (QACs), triclosan, metal ions, oxides, some inorganic compounds, salts (e.g., Ag, TiO2, Cu, Ni, Pd, Ag(I), Pd(II) complexes), and natural polymers (e.g., chitosan, chitin).

[0004] Among the above compounds, QACs are widely used on cotton, polyester, nylon, wool, etc. The antibacterial effect of QACs is highly dependent on the length of the alkyl chain and the number of cationic ammonium groups.

[0005] In the manufacturing process of some industrial textiles, such as denim, washing is an unavoidable step in the manufacture of garments, so it is easy to understand that the applied antimicrobial substance needs to exhibit strong adhesion to the textile.

[0006] Currently available antimicrobial agents do not meet necessary stability requirements, and either easily leach from the textile surface, and / or exhibit hydrolytic instability, and / or lose antimicrobial activity over time, and / or reduce the tensile strength of the textile.

[0007] (2003) by Kazank et al. discloses that polyurethanes are obtained by copolymerizing monomers containing hydroxyl functional groups with monomers containing quaternized tertiary amine moieties, followed by crosslinking of the hydroxyl functional groups present in the copolymer with isocyanates to form polyurethane films. As described in (2003), this insoluble polyurethane film adheres to the surface of undyed indigo fabrics through positive-negative charge interactions between the quaternized ammonium functional groups and the negatively charged indigo molecules. However, this interaction is weak, resulting in leaching of the coating during use and washing.

[0008] Pilling is a common defect in textiles caused by wear, washing, etc., which damages the fibers over time. Pilling is a significant problem that needs to be solved in the textile industry.

[0009] Therefore, there is a need for new antimicrobial substances that overcome the above-mentioned drawbacks of the prior art and that can impart more interesting and useful properties to textiles, such as anti-pilling effects. [Prior art documents] [Non-patent literature]

[0010] [Non-Patent Document 1] Kazanc et al., Marmara Journal of Pure and Applied Sciences, 2015, Special Feature-I, pp. 49-52 Summary of the Invention [Problem to be solved by the invention]

[0011] A first object of the present invention is to provide a method for imparting antimicrobial and antipilling properties to textiles and improving dye uptake into textiles by treating them with known and novel copolymers and diisocyanates.

[0012] Another object of the present invention is to provide novel copolymers and their use with the methods of the present invention, as well as to provide textiles, garments and yarns based on the methods of the present invention.

[0013] A further object of the present invention is to provide textiles, preferably denim, whose hydroxyl groups are covalently bonded to these known and novel copolymers through urethane crosslinks.

[0014] These and other objectives are achieved by the invention disclosed and claimed herein. [Means for solving the problem]

[0015] According to one aspect, the present invention relates to a method for imparting antimicrobial and anti-pilling effects to textiles and improving dye uptake into said textiles, said method comprising: (i) treating the textile with an aqueous solution containing the following a) and b): a) Monomers of general formula (I) TIFF0007826591000001.tif3064(I) or a mixture thereof, and a monomer of general formula (II) TIFF0007826591000002.tif3058(II) or at least one copolymer made from a mixture thereof, where: - each X is independently selected from the following chain (A) or chain (B): TIFF0007826591000003.tif2051(A) TIFF0007826591000004.tif18116(B) - the asterisks indicate bonds to the oxygen and nitrogen atoms of the monomers of formula (I) and formula (II), - each n is independently an integer from 1 to 10; Alk is a C1-C4 alkyl group; wherein the tertiary amino group in the above formula (I) is optionally partially quaternized with a halo long-chain alkyl group; b) at least one aliphatic or cycloaliphatic diisocyanate; (ii) optionally drying and / or fixing the textile product; Contains:

[0016] According to a preferred embodiment, the method of the invention is characterized by the fact that the copolymer (a) and the textile product are at least partially covalently bonded by urethane crosslinks imparted by the aliphatic or cycloaliphatic diisocyanate (b).

[0017] According to the method of the present invention, as shown in FIG. 1, treatment of a textile with components (a) and (b) forms urethane crosslinks between the free hydroxyl groups in the monomer of general formula (II) and the free hydroxyl groups present in the textile.

[0018] As used herein, the term "Alk" refers to a linear or branched saturated C1-C4 alkyl group, preferably a linear alkyl group, more preferably a methyl or ethyl group, with a methyl group being particularly preferred.

[0019] According to a preferred embodiment, n is an integer between 1 and 8, for example 1, 2, 3 or 4, more preferably n is 1 or 2, advantageously n is 1.

[0020] The phrase "the tertiary amino groups of formula (I) are optionally partially quaternized with halo-long chain alkyl groups" means that quaternized ammonium groups may be present in the copolymer, which is achieved by reacting the copolymer with halo-long chain alkyl groups, so that the monomer of formula (I) has the formula (Ia) It becomes a monomer of TIFF0007826591000005.tif3075 (Ia) where X and Alk are as defined above, and Alk′ is a C6-C 22 Alkyl groups, preferably C8 to C 20 Alkyl groups, such as C 10 , C 12 , C 14 , C 16 or C 18 and Hal - is a halogen counterion, e.g., Br - or Cl - , preferably Br - This shows:

[0021] The expression "aliphatic or cycloaliphatic diisocyanate" will be apparent to those skilled in the art and, as used herein, preferably includes hexamethylene diisocyanate, isophorone diisocyanate, and methylene-bis(4-cyclohexylisocyanate), with hexamethylene diisocyanate being particularly preferred. However, other diisocyanates may also be used in the process of the present invention, provided they are capable of forming urethane crosslinks that react with the hydroxyl groups of the copolymer and the hydroxyl groups of the textile.

[0022] According to the present invention, the diisocyanate may be a blocked diisocyanate such as a diisocyanate blocked with dimethylpyrazole, caprolactam, butanone oxime, 1,2-pyrazole, 1,2,4-triazole, diisopropylamine, 3,5-dimethylpyrazole, and diethyl malonate. Blocked diisocyanates are known in the art, and a person skilled in the art can easily select a suitable diisocyanate for carrying out the method of the present invention.

[0023] The above-mentioned monomers and compounds are known in the art and can be prepared by known and conventional processes.

[0024] The term "textile" as used herein refers to any material suitable for preparing fabrics and garments, and includes fibers, filaments, yarns, fabrics, fabrics that can be dyed, and any textile product, such as garments, textiles, and fabric-based articles. The expression "fabric ready for dyeing" refers to fabric that has been through the desizing, mercerizing (or bleaching) and washing steps.

[0025] According to a preferred embodiment, the textile of the present invention is an indigo textile, such as denim.

[0026] According to a preferred embodiment, the molar ratio of (monomer of formula (I)) / (monomer of formula (II)) is about (95-85) / (5-15), preferably about 90 / 10.

[0027] According to a preferred embodiment, 20-40%, most preferably about 30%, of the tertiary amino groups in the copolymer are quaternized.

[0028] It is preferred that only one type of monomer of formula (I) and only one type of monomer of formula (II) is present in the copolymer.

[0029] Preferably, only one diisocyanate is used in the process of the present invention.

[0030] According to a preferred embodiment, as mentioned above, the present invention relates to a method for imparting antibacterial and anti-pilling effects to a textile article, the method comprising the step of coating the textile article with an aqueous solution comprising the following a') and b'): a') is a copolymer of at least 2-(dimethylamino)ethyl methacrylate (DMAEMA) and 2-hydroxyethyl methacrylate (HEMA), optionally quaternized with a halo long chain alkyl group; b') is at least one aliphatic or cycloaliphatic diisocyanate for forming urethane crosslinks between the free hydroxyl groups of HEMA and the free hydroxyl groups present in the textile; DMAEMA has the following chemical formula (I'): TIFF0007826591000006.tif2976(I') HEMA has the following chemical formula (II'): TIFF0007826591000007.tif2861(II')

[0031] According to a preferred embodiment, the molar ratio of (DMAEMA / HEMA) is about (95-85) / (5-15), preferably about 90 / 10.

[0032] According to a preferred embodiment, 20-40% of the tertiary amino groups are quaternized as described above, most preferably about 30%.

[0033] The preferred embodiments of the methods described above also apply to the methods involving DMAEMA and HEMA described above.

[0034] In addition to the copolymer (a) and diisocyanate (b) described above, the aqueous solution used in the method of the present invention (herein referred to as the "coating composition") may further contain other components, such as wetting agents and thickeners, such as wetting agents commercially available under the trade names Leonil KS, Mersitol 2334 AQ, and Mercerol QWLF, preferably used at about 1 vol% of the total solution volume, and / or thickeners commercially available under the trade names Pirusulan DCA 24 ST and Pirusulan DCA 130, preferably used to adjust the viscosity to between 0.002 and 0.0024 Pascal seconds (Pa·s) (20 to 24 decicentipoise (dcP)).

[0035] As used herein, the term "coating" refers to any method by which a solution can be applied to a textile, including, but not limited to, padding, dipping, printing, and the like.

[0036] After applying the aqueous solution to the textile, the coated fabric is dried, for example, by heating. The drying temperature depends on the type of textile. For example, in the case of denim, the drying process can be carried out at 100-160°C, e.g., 150°C, for several minutes. Alternatively, the coated textile can be fixed at a higher temperature, e.g., 170-190°C, for one minute or more.

[0037] According to a preferred embodiment, the copolymer concentration in the aqueous solution is from about 2 to about 15 g / L.

[0038] As described above, in the method of the present invention, it has surprisingly been found that when an aqueous solution containing copolymer (a) and diisocyanate (b) (or (a') and (b')) is applied to a textile, the diisocyanate molecules react with either the hydroxyl groups present in the copolymer or the hydroxyl groups present on the surface of the textile, thereby forming urethane crosslinks that form covalent bonds between the copolymer and the textile.

[0039] This allows for the provision of a stable copolymer coating on textiles that will not leach out, even after multiple washes (industrial washes such as stonewashing and home laundering).

[0040] This copolymer coating offers very interesting benefits, such as antibacterial and anti-pilling effects due to the presence of quaternized ammonium groups.

[0041] It has also been observed that coatings of the copolymers of the present invention can be activated to increase dye uptake by the copolymer coating, resulting in darker shades.

[0042] The reaction for preparing the copolymer of the present invention can be carried out according to the method described in Non-Patent Document 1. As described there, a preformed insoluble polyurethane film comprising a HEMA / DMAEMA copolymer crosslinked with an aliphatic isocyanate adheres to the surface of undyed indigo fabric through positive and negative charge interactions. In contrast, the method of the present invention involves applying an aqueous solution comprising a DMAEMA / HEMA copolymer and an isocyanate to a textile to obtain a coating that is at least partially covalently bonded to the textile through urethane crosslinking.

[0043] Alternative processes that can be implemented are shown in the detailed description below.

[0044] In another aspect, the present invention relates to novel copolymers made from DMAEMA and HEMA, characterized in that the molar ratio (DMAEMA / HEMA) is (95-85) / (5-15), preferably about 90 / 10, and in that 20-40%, most preferably about 30%, of the tertiary amino groups are quaternized with the substituent (C) as described above.

[0045] According to another aspect, the present invention also relates to the use of at least one copolymer, preferably the novel copolymer, in the coating of textiles according to the method of the present invention, as described herein.

[0046] According to another aspect, as described herein, the present invention also relates to the use of an aqueous solution of at least one copolymer comprising the novel copolymer of the present invention and at least one aliphatic or cycloaliphatic diisocyanate in the coating of textiles by the method of the present invention.

[0047] According to another aspect, as described herein, the present invention also relates to the use of an aqueous solution of at least one copolymer (herein "coating composition") comprising the novel copolymer of the present invention and at least one aliphatic or cycloaliphatic diisocyanate to impart antimicrobial and anti-pilling effects to textiles.

[0048] In another aspect, the present invention relates to the use of an aqueous solution of at least one copolymer, as described herein, comprising the novel copolymer of the present invention and at least one aliphatic or cycloaliphatic diisocyanate, to improve dye uptake in textiles, preferably denim, thereby allowing for the production of darker shades.

[0049] According to another aspect, the present invention relates to textiles, preferably denim, fabrics and garments, as well as yarns, which have been treated with the process of the present invention.

[0050] According to another aspect, the present invention relates to a textile, preferably denim, the hydroxyl groups of which are at least partially covalently bonded to a copolymer consisting of at least a monomer of formula (I) or (I') and at least a monomer of formula (II) or (II') by urethane crosslinking, as described above.

[0051] According to a preferred embodiment, the present invention relates to textiles, preferably fabrics and garments, in particular denim fabrics and denim garments, the hydroxyl groups of which are at least partially covalently bonded to a copolymer of at least a monomer of formula (I) or (I') and at least a monomer of formula (II) or (II') by urethane crosslinks, as described above, which are formed by at least one aliphatic or cycloaliphatic diisocyanate, as described herein.

[0052] Experimental tests were conducted to demonstrate the antimicrobial effectiveness of the coatings of the present invention, and are described in detail in the Detailed Description below.

[0053] The anti-pilling effect was evaluated by experts on the detection and measurement methods of anti-pilling effect, by which the coating composition showed very interesting results.

[0054] The following "Description of the Preferred Embodiments" illustrates typical embodiments of the present invention and is not intended to limit the embodiments. [Brief explanation of the drawings]

[0055] [Figure 1] 1 is a schematic diagram of the reactions occurring in the process of the present invention, where x and y represent the number of monomers in the copolymer. [Figure 2A] 1 shows the antibacterial efficacy of representative quaternized copolymers of the present invention against Staphylococcus aureus. [Figure 2B] 1 shows the antibacterial effect of representative quaternized copolymers of the present invention against E. coli. DETAILED DESCRIPTION OF THE INVENTION

[0056] [Example 1] Preparation of copolymers A monomer solution containing 100 mmol of HEMA and 900 mmol of DMAEMA was prepared, and 10 vol% of this solution was added to a reactor set at 70 °C. Next, 50 ml of distilled water was added to the reactor, and a solution consisting of the monomer mixture, ammonium persulfate (22 g of ammonium persulfate dissolved in 100 ml of water), and sodium metabisulfate (19 g of sodium metabisulfate dissolved in 100 ml of water) was added at 2 ml / min while stirring. The copolymer was recovered from the reactor and washed with hot water (70-80 °C) to remove unreacted monomer, ammonium persulfate, and sodium metabisulfate.

[0057] [Example 2] Quaternization Process The 25-30% of the DMAEMA residue present in the copolymer of Example 1 is quaternized with an alkyl halide by the following procedure: 50 g of the copolymer is dissolved in 300 ml of absolute ethanol, 75 mmol of an alkyl halide, preferably 1-bromodecane, is added, and the solution is then stirred at room temperature for 24 hours. The ethanol is evaporated and the quaternized copolymer is recovered by conventional workup.

[0058] [Example 3] Coating Process A coating solution is prepared using water, the quaternized copolymer of Example 2, hexamethylene diisocyanate, a wetting agent, and a thickener as follows: 2.5 g of the quaternized copolymer (10% of the HEMA in the copolymer) is dissolved in 1 L of water along with 50-75 mg of diisocyanate, 6-8 g of wetting agent, and a thickener to adjust the viscosity to 0.002-0.0024 Pascal seconds (Pa·s) (20-24 decicentipoise (dcP)). The solution is then applied to the fabric. This can be done, for example, by coating or impregnation. In the coating method, a thickener can be added to the solution to achieve the desired viscosity. In contrast, the impregnation process does not require a thickener. A sanding machine can also be used to apply the solution to the fabric. The coated fabric is dried at 150°C for approximately 3 minutes, and then set at 170°C for approximately 1 minute.

[0059] [Example 4] Antibacterial effect The antibacterial effects of the copolymer of Example 2 and fabrics coated therewith were confirmed against the following bacteria in accordance with ASTM E2149-01. - ATCC® 35218 (E. coli) - ATCC® 6538 (Staphylococcus aureus)

[0060] The results, as shown in Figures 2A and 2B, indicate that the quaternized copolymer of Example 2 has antibacterial effects against Staphylococcus aureus and Escherichia coli.

[0061] Figures 2A and 2B show two Petri dishes, each divided into eight sections. In both Figures 2A and 2B, each of the eight sections of the Petri dish corresponds to a different concentration of copolymer tested. As can be seen from Figures 2A and 2B, the tested concentrations of the quaternized copolymer of Example 2 were 0.0195 g / L, 0.039 g / L, 0.078 g / L, 0.156 g / L, 0.3125 g / L, 0.625 g / L, 1.25 g / L, and 2.5 g / L.

[0062] As can be seen from Figures 2A and 2B, the antibacterial effect against Staphylococcus aureus is achieved even at very low copolymer concentrations (starting from 0.0195 g / L), while the antibacterial effect against Escherichia coli starts from 1.25 g / L and is very satisfactory at 2.5 g / L.

Claims

1. A method for imparting antibacterial effect to a textile product having a hydroxyl group, comprising: (i) treating the textile with an aqueous solution comprising at least one copolymer (a) and at least one aliphatic or cycloaliphatic diisocyanate (b); and optionally, step (ii) of drying and / or fixing the textile product, The at least one copolymer (a) is made from a monomer of general formula (I) or a mixture thereof, and a monomer of general formula (II) or a mixture thereof, 【Chemistry 1】 (I) 【Chemistry 2】 (II) where: Each X is independently selected from the following chains (A) and (B): 【Transformation 3】 (A) 【Chemistry 4】 (B) The asterisk indicates a bond to an oxygen atom or a nitrogen atom of the monomer of the general formula (I) and the general formula (II), n is independently an integer from 1 to 10, Alk is C １ -C ４ is an alkyl group, 20 to 40% of the tertiary amino groups in the copolymer (a) are C ６ -C ２２ Partially quaternized with halo long chain alkyl groups having alkyl groups, Step (i) of treating the textile with the aqueous solution causes the at least one aliphatic or cycloaliphatic diisocyanate (b) to react with either the hydroxyl groups present in the at least one copolymer (a) or the hydroxyl groups present on the surface of the textile, thereby forming urethane crosslinks that covalently bond the at least one copolymer (a) to the textile; The method, wherein the molar ratio of the monomer of the general formula (I) to the monomer of the general formula (II) (monomer of the general formula (I)) / (monomer of the general formula (II)) is (95 to 85) / (5 to 15).

2. The Alk is a linear or branched saturated C １ -C ４ 2. The method of claim 1, wherein the alkyl group is an alkyl group.

3. The method according to claim 1 or 2, wherein n is an integer of 1 to 8.

4. wherein the tertiary amino group of the general formula (I) is quaternized to provide a monomer of the following general formula (Ia): 【Transformation 5】 (Ia) where X and Alk are as defined above and Alk′ is C ６ -C ２２ is an alkyl group, and Hal － 4. The method according to claim 1, wherein denotes a halogen counterion.

5. 5. The method according to claim 1, wherein the aliphatic or alicyclic diisocyanate (b) is selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, methylene-bis(4-cyclohexylisocyanate) and blocked aliphatic or alicyclic diisocyanates.

6. 6. The method according to any one of claims 1 to 5, wherein the copolymer (a) is made from 2-(dimethylamino)ethyl methacrylate (DMAEMA) and 2-hydroxyethyl methacrylate (HEMA).

7. The method described in claim 6, characterized in that the molar ratio of the 2-(dimethylamino)ethyl methacrylate (DMAEMA) to the 2-hydroxyethyl methacrylate (HEMA) (the 2-(dimethylamino)ethyl methacrylate (DMAEMA)) / (2-hydroxyethyl methacrylate (HEMA)) is (95 to 85) / (5 to 15).

8. 8. The method according to any one of claims 1 to 7, wherein the textile product is selected from any material suitable for preparing fabrics and garments, yarns, fabrics ready to be dyed, any textile product, and garment product.

9. 9. The method of claim 8, wherein the textile is denim.

10. 10. The method according to claim 1, wherein the copolymer (a) and the textile product are at least partially covalently bonded by urethane crosslinks provided by the aliphatic or cycloaliphatic diisocyanate (b).

11. A method for producing textiles or denim treated by the method according to any one of claims 1 to 7.

12. A textile product comprising fibers or filaments having hydroxyl groups, at least a portion of the hydroxyl groups of the textile form covalent bonds to the copolymer via urethane crosslinking; The copolymer comprises a monomer of the following general formula (I) or (I') and at least a monomer of the following general formula (II) or (II'): 【Transformation 6】 (I) 【Transformation 7】 (I') 【Transformation 8】 (II) 【Chemistry 9】 (II') where: Each X is independently selected from the following chain (A) or chain (B): 【Chemistry 10】 (A) 【Chemistry 11】 (B) The asterisk indicates a bond to an oxygen atom or a nitrogen atom of the monomer of the general formula (I) and the general formula (II), n is independently an integer from 1 to 10, Alk is a C 1 -C 4 alkyl group; 20 to 40% of the tertiary amino groups of the general formula (I) or (I') are partially quaternized with halo long-chain alkyl groups having C 6 -C 22 alkyl groups; A textile product characterized in that the molar ratio of the monomer of the general formula (I) or (I') to the monomer of the general formula (II) or (II') (monomer of the general formula (I) or (I')) / (monomer of the general formula (II) or (II')) is (95 to 85) / (5 to 15).

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