Methods for imparting antibacterial and anti-pilling effects to textiles and novel copolymers / textiles, and methods for improving the incorporation of dyes into textiles and novel copolymers / textiles.

Abstract

The present invention provides a method for imparting antibacterial and anti-pilling effects to textile products and improving the incorporation of dyes into the textile products, as well as a novel copolymer and a novel textile product used in the method. [Solution] (i) A step of treating a textile product with an aqueous solution containing a) and b) below, a) For example, at least one copolymer made from 2-(dimethylamino)ethyl methacrylate (DMAEMA) and 2-hydroxyethyl methacrylate (HEMA), b) at least one aliphatic or alicyclic diisocyanate, (ii) a step of drying and / or fixing the textile product, if necessary. A method characterized by including the following.

Description

[Technical Field]

[0001] The present invention relates to a method for imparting antibacterial and anti-pilling effects to textiles, and to a method for improving the incorporation of dyes into textiles. The present invention also relates to novel copolymers and novel textiles used in the method of the present invention. [Background technology]

[0002] Antimicrobial, and especially antimicrobial, textiles are known in the art and are usually prepared by coating the textile or yarn with an antimicrobial substance. Of course, the antimicrobial substance must be non-toxic and non-allergenic to human skin.

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

[0004] Among the compounds mentioned above, QACs are widely used in cotton, polyester, nylon, wool, and other materials. The antibacterial effect of QACs largely depends on the length of the alkyl chain and the number of cationic ammonium groups.

[0005] In the manufacturing process of some industrial textile products, such as denim, washing is an unavoidable step in garment production, so it is easy to understand that the antimicrobial substances applied need to exhibit strong adhesion to the textiles.

[0006] Currently available antimicrobial substances do not meet the necessary stability requirements, readily leach from the surface of textiles, exhibit hydrolytic instability, and / or decrease in antimicrobial activity over time, and / or reduce the tensile strength of textiles.

[0007] Non-Patent Document 1 by Kazank et al. discloses that polyurethane can be obtained by copolymerization of a monomer having a hydroxyl functional group and a monomer having a quaternized tertiary amine moiety, and that a polyurethane film is formed by subsequent crosslinking of the hydroxyl functional groups present in the copolymer with an isocyanate. As described in Non-Patent Document 1, this insoluble polyurethane film adheres to the surface of undyed indigo fabric through positive and negative charge interactions between the quaternized ammonium functional groups and negatively charged indigo molecules. However, this interaction is weak, so the attached coating leaches out with use or washing.

[0008] Pilling is a common defect in textiles caused by wear and washing, resulting in the deterioration of fibers over time. Pilling is a significant problem that needs to be addressed in the field of textiles.

[0009] Therefore, there is a need for novel antimicrobial substances that can overcome the shortcomings of the prior art described above and impart even more interesting and useful properties, such as anti-pilling effects, to textile products. [Prior art documents] [Non-patent literature]

[0010] [Non-Patent Document 1] Kazanc et al., *Marmara Journal of Pure and Applied Sciences*, 2015, Special Issue I, pp. 49-52. [Overview of the project] [Problems that the invention aims to solve]

[0011] The first objective of the present invention is to provide a method for imparting antibacterial and anti-pilling effects to textile products and improving dye uptake into textile products by treating them with known and novel copolymers and diisocyanates.

[0012] Another object of the present invention is to provide novel copolymers, to use these copolymers by means of the method of the present invention, and to provide textiles, clothing and threads based on the method of the present invention.

[0013] A further object of the present invention is to provide a textile, preferably denim, the hydroxyl groups of which form a covalent bond with these known and novel copolymers by means of urethane crosslinking.

[0014] These objects and other objects can be achieved by the invention disclosed in the specification and claims of the present application.

Means for Solving the Problems

[0015] According to one aspect, the present invention relates to a method for imparting an antibacterial effect and an anti-pilling effect to a textile and improving the uptake of a dye into the textile, the method comprising: (i) treating the textile with an aqueous solution containing the following a) and b); a) a monomer of general formula (I)

Chemical formula

[0016] In a preferred embodiment, the method of the present invention is characterized by the fact that the copolymer (a) and the fibrous product are at least partially covalently bonded by urethane crosslinking imparted by an aliphatic or alicyclic diisocyanate (b).

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

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

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

[0020] The expression "the tertiary amino group of formula (I) is optionally partially quaternized with a halo long-chain alkyl group" means that a quaternized ammonium group may be present in the copolymer, which is achieved by the reaction of the copolymer with a halo long-chain alkyl group, and as a result, the monomer of formula (I) becomes a monomer of formula (Ia). [Chemical formula] (Ia) where X and Alk are as described above, and Alk' is a C6 - C - , 18 ,

[0021] , - , , , 14 , 16 , , , 10 , , 12 , , 22 , , 20 , - ,

[0022] , - , , alkyl group, preferably a C8 - C 20 alkyl group, for example C 10 , C 12 , C 14 , C 16 or C 18 and Hal - is a halogen counterion, for example, Br - or Cl - , preferably Br - is shown.

[0021] The expression "aliphatic or alicyclic diisocyanate" is self - evident to those skilled in the art, and in this specification, it preferably includes hexamethylene diisocyanate, isophorone diisocyanate and methylene - bis(4 - cyclohexyl isocyanate), and hexamethylene diisocyanate is particularly preferred. However, other diisocyanates can also be used in the method of the present invention as long as they can form urethane cross - links 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 dimethylpyrazole, caprolactam, butanone oxime, 1,2-pyrazole, 1,2,4-triazole, diisopropylamine, 3,5-dimethylpyrazole, and diethyl malonate-blocked diisocyanates. Blocked diisocyanates are known in the art, and those skilled in the art can easily select a suitable diisocyanate to carry out the method of the present invention.

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

[0024] In this specification, the term “textiles” refers to any material suitable for preparing fabrics and garments, and includes fibers, filaments, yarns, fabrics, fabrics that can be dyed, and any textile products such as garments, cloths and fabric-based articles. The expression “fabric ready to be dyed” means a fabric that has undergone desizing, mercerizing (or bleaching) and washing processes.

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

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

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

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

[0029] In the method of the present invention, it is preferable to use only one type of diisocyanate.

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

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

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

[0033] Preferred embodiments of the above-described method also apply to the method comprising DMAEMA and HEMA as described above.

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

[0035] In this specification, the term "coating" means all methods to which a solution can be applied to a textile product, including but not limited to padding, dipping, and printing.

[0036] After applying the above 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, for example, 150°C, for several minutes. Alternatively, the coated textile may be fixed at a higher temperature, such as 170-190°C, for one minute or more.

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

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

[0039] This allows for the application of a stable copolymer coating to textiles, which will not leach out even after multiple washes (industrial cleaning such as stonewashing and home washing).

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

[0041] Furthermore, it has been observed that the copolymer coating of the present invention can produce a deeper color because the copolymer coating activates the material, increasing its ability to incorporate dyes.

[0042] The reaction for preparing the copolymer of the present invention can be carried out according to Non-Patent Document 1. As described in that document, a pre-formed insoluble polyurethane film containing a HEMA / DMAEMA copolymer crosslinked with an aliphatic isocyanate adheres to the surface of an undyed indigo fabric by positive and negative charge interactions. Conversely, the method of the present invention includes the step of applying an aqueous solution containing the DMAEMA / HEMA copolymer and an isocyanate to a textile product to obtain a coating in which at least partially covalent bonds are formed on the textile product by urethane crosslinking.

[0043] Possible alternative processes are shown in the following "Modes for Carrying Out the Invention".

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

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

[0046] In 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 alicyclic diisocyanate in coating textile products by the method of the present invention.

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

[0048] In another aspect, the present invention 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 alicyclic diisocyanate to improve dye uptake in textiles, as described herein. This allows for darker shades to be obtained. Denim is preferred for the textile.

[0049] In another embodiment, the present invention relates to textile articles, preferably denim, fabrics and garments, and yarns, processed by the method of the present invention.

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

[0051] According to preferred embodiments, the present invention relates to textiles, preferably fabrics and garments, in particular denim fabrics and denim garments, wherein, as described above, the hydroxyl groups of the textiles are at least partially covalently bonded to a copolymer consisting of at least monomers of formula (I) or (I') and at least monomers of formula (II) or (II') by urethane crosslinking. The urethane crosslinking is generated by at least one aliphatic or alicyclic diisocyanate, as described herein.

[0052] Experimental tests were conducted to demonstrate the antibacterial effect of the coating of the present invention. These tests are described in detail in the "Modes for Carrying Out the Invention" section below.

[0053] The anti-pilling effect was evaluated by experts in methods for detecting and measuring anti-pilling effects. Using this method, the coating composition showed very interesting results.

[0054] The following "Modes for Carrying Out the Invention" are illustrative of typical embodiments of the present invention and do not limit the embodiments. [Brief explanation of the drawing]

[0055] [Figure 1] This is a schematic diagram of the reaction that occurs by the method of the present invention, where x and y represent the number of monomers in the copolymer. [Figure 2A] This demonstrates the antibacterial effect of a representative quaternary copolymer of the present invention against Staphylococcus aureus. [Figure 2B] This demonstrates the antibacterial effect of a representative quaternary copolymer of the present invention against Escherichia coli. [Modes for carrying out the invention]

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

[0057] [Example 2] Grade 4 process 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 anhydrous ethanol, and 75 mmol of an alkyl halide, preferably 1-bromodecane, is added. The solution is then stirred at room temperature for 24 hours. The ethanol is evaporated using a conventional work-up procedure to recover the quaternized copolymer.

[0058] [Example 3] Coating process A coating solution is prepared using water, the quaternary copolymer from Example 2, hexamethylene diisocyanate, a wetting agent, and a thickening agent as follows: 2.5 g of the quaternary copolymer (10% of the HEMA in the copolymer) is dissolved in 1 L of water with 50-75 mg of diisocyanate, 6-8 g of wetting agent, and a thickening agent to adjust the viscosity to 0.002-0.0024 Pascal seconds (Pa·s) (20-24 decicentopoise (d·cP)). Next, this solution is applied to the dough. This can be done, for example, by coating or impregnation. In the coating method, a thickening agent may be added to the solution to obtain the desired viscosity. In contrast, the impregnation process does not require a thickening agent. A sun horizing machine can also be used to apply the solution to the dough. The coated dough is dried at 150°C for about 3 minutes, and then fixed at 170°C for about 1 minute.

[0059] [Example 4] Antibacterial effect The antimicrobial effect of the copolymer of Example 2 and the fabric coated therewith was confirmed against the following bacteria, based on ASTM E2149-01. - ATCC (Registered Trademark) 35218 (Escherichia coli) - ATCC(registered trademark) 6538 (Staphylococcus aureus)

[0060] The results, as shown in Figures 2A and 2B, indicate that the quaternary 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 the copolymer tested. As can be seen from Figures 2A and 2B, the test concentrations of the quaternary 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, antibacterial effects against Staphylococcus aureus are achieved even at very low copolymer concentrations (starting from 0.0195 g / L), and antibacterial effects against Escherichia coli start at 1.25 g / L and are very satisfactory at 2.5 g / L.

Claims

1. A method for imparting antibacterial and anti-pilling effects to textile products and improving the incorporation of dyes into said textile products, (i) A step of treating the textile product with an aqueous solution containing a) and b) below, a) Monomer of general formula (I) 【Chemistry 1】 (I) or a mixture thereof and monomers of general formula (II) 【Chemistry 2】 (II) or at least one copolymer made from a mixture thereof, Here, - Each X is independently selected from either the (A) or (B) chain below. 【Transformation 3】 (A) 【Chemistry 4】 (B) - The asterisk indicates the bonding between the monomers of formulas (I) and (II) and the oxygen and nitrogen atoms. - n is an integer between 1 and 10, independently of each other. - Alk is C １ -C ４ It is an alkyl group, Here, the tertiary amino group in formula (I) is partially quaternized with a halo-long-chain alkyl group as needed. b) At least one aliphatic or alicyclic diisocyanate, (ii) a step of drying and / or fixing the textile product, if necessary. A method characterized by including the following.

2. The Alk is a linear or branched saturated C １ -C ４ The method according to claim 1, characterized in that the alkyl group is preferably a methyl group.

3. The method according to 1 or 2, characterized in that n is an integer from 1 to 8, preferably 1.

4. The nitrogen atom in formula (I) is quaternized to provide the monomer of formula (Ia), 【Transformation 5】 (Ia) Here, X and Alk are as described above, and Alk’ is a C ６ -C ２２ alkyl group, preferably a C ８ to C ２０ alkyl group, for example C １０ , C １２ , C １４ , C １６ or C １８ , and Hal － is a halogen counterion, for example, Br － or Cl － , preferably Br － The method according to any one of claims 1 to 3, characterized in that it is shown.

5. The method according to any one of claims 1 to 4, characterized in that the aliphatic or alicyclic diisocyanate is selected from hexamethylene diisocyanate, isophorone diisocyanate, methylene-bis(4-cyclohexyl isocyanate), and blocked aliphatic or alicyclic diisocyanate.

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

7. The method according to any one of claims 1 to 6, characterized in that the molar ratio of (monomer of formula (I) / monomer of formula (II)) is about (95 to 85) / (5 to 15), preferably about 90 / 10.

8. The method according to any one of claims 1 to 7, characterized in that 20 to 40%, most preferably about 30%, of the tertiary amino groups in the copolymer are quaternized.

9. The method according to any one of claims 1 to 8, characterized in that the textile article is selected from any material, yarn, fabric ready for dyeing, any textile product, and garment product suitable for preparing fabrics and garments.

10. The method according to 9, characterized in that the textile product is denim.

11. The method according to any one of claims 1 to 10, characterized in that the copolymer (a) and the fiber product are at least partially covalently bonded by urethane crosslinking imparted by the aliphatic or alicyclic diisocyanate (b).

12. A copolymer comprising DMAEMA and HEMA, wherein the molar ratio of (DMAEMA / HEMA) is (95-85) / (5-15), preferably about 90 / 10, and 20-40%, most preferably about 30%, of the tertiary amino groups are quaternized as defined in claim 4.

13. Use of at least one copolymer according to claims 1 to 8 or claim 11 for imparting antibacterial and anti-pilling effects to textiles and improving the incorporation of dyes into textiles.

14. The use of aqueous solutions according to claims 1 to 8 for imparting antibacterial and anti-pilling effects to textile products and improving the absorption of dyes by textile products.

15. To impart antibacterial and anti-pilling effects to textiles and to improve dye absorption by textiles, use of an aqueous solution comprising at least one copolymer according to claim 12 and at least one aliphatic or alicyclic diisocyanate.

16. A textile product, preferably denim, treated by the method according to any one of claims 1 to 8.

17. A textile product comprising fibers or filaments having hydroxyl groups, A textile product characterized in that at least a portion of the hydroxyl groups of the textile product are covalently bonded by urethane crosslinking to a copolymer consisting of a monomer of formula (I), (Ia), or (I') and a monomer of formula (II) or (II') from among the formulas described in any one of claims 1 to 4 and shown below. Here, Equation (I') is DMAEMA. 【Transformation 6】 (I') Equation (II') is HEMA. 【Transformation 7】 (II')

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