A method for cool antibacterial finishing of cotton fabric

Abstract

The invention belongs to the field of textile engineering and discloses a method for cool and antibacterial finishing of cotton fabrics. The method comprises: oxidizing the cotton fabric, grafting casein phosphopeptide (CPP), grafting ε-polylysine (ε-PLL) onto the CPP through acylation, and finally washing and drying. After the surface of the cotton fabric is grafted and modified by the present invention, the cool comfort and antibacterial performance of the fabric are improved.

Description

Technical Field

[0001] The invention relates to the field of textile engineering, and in particular to a method for cool antibacterial finishing of cotton fabrics. Background Art

[0002] As people's requirements for clothing increase, single-function cool fabrics can no longer meet consumer demand, and multifunctional composite cool fabrics will be the future development trend. Cool fabrics are mainly used in summer products. In addition to good moisture absorption and perspiration, cooling functions, they should also have functions such as sterilization, deodorization and sun protection. Therefore, in the future development of cool fabrics, fabrics should be given more functions to meet consumers' demand for multi-layered clothing. Summary of the invention

[0003] In view of this, the present invention provides a method for cool antibacterial finishing of cotton fabrics. The cotton fabric obtained by the finishing method can rely on the ε-PLL on the surface to absorb moisture, increase its thermal conductivity to obtain a cool feeling, and at the same time can achieve Ag + and ε-PLL have dual bactericidal effects.

[0004] In order to solve the above technical problems, the present invention discloses a method for cool antibacterial finishing of cotton fabric, comprising the following steps:

[0005] S1: soak the cotton fabric in sodium periodate solution for reaction, then wash and dry;

[0006] S2: soaking the cotton fabric in step S1 in an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate containing calixarene, CPP and biotin silver nanoparticles, reflux reaction, washing with water and drying; the calixarene is one of calix[6]arene, 4-tert-butylcalix[6]arene or 4-sulfonylcalix[6]arene;

[0007] S3: soaking the cotton fabric in step S2 in pyridine containing ε-PLL and trichloro-s-triazine, dripping triethylamine while stirring under ultraviolet irradiation, and then washing and drying after reaction.

[0008] Preferably, in step S1, the concentration of the sodium periodate solution is 100-120 g / L, and the pH value is 1.0-2.5.

[0009] Preferably, in step S1, the immersion bath ratio is 30:1-50:1, the temperature is 30-40°C, and the time is 3-6h.

[0010] Preferably, in step S2, the average particle size of the biotin silver nanoparticles is 5-100 nm.

[0011] Preferably, in step S2, the amounts of calixarene, CPP and silver biotin nanoparticles are 80-200 mg / m2 Cotton fabric, 5-8g / m 2 Cotton fabric and 300-500mg / m 2 Cotton fabric.

[0012] Preferably, in step S2, the reflux reaction temperature is 60-85° C. and the time is 5-8 h.

[0013] Preferably, in step S3, the amount of ε-PLL, trichlorotriazine and triethylamine is 10-20 g / m 2 Cotton fabric, 0.92-1.84g / m 2 Cotton fabric and 0.50-1.01g / m 2 Cotton fabric.

[0014] Preferably, in step S3, the ε-PLL weight average molecular weight is 3600-4300, and the ultraviolet irradiation intensity is 250-400 μW / cm 2 .

[0015] Preferably, in step S3, the reaction temperature is -10-4°C and the reaction time is 5-10 min.

[0016] Compared with the prior art, the finishing method of the present invention utilizes the hydroxyl groups on the surface of the cotton fabric to be oxidized and react with the amino groups in CPP under the catalysis of biotin silver nanoparticles to form a Schiff base. The generated silver ions can be converted into central atoms and form coordination bonds with the Schiff base, stabilizing its structure and preventing it from hydrolysis. Afterwards, ultraviolet irradiation is used to activate the tyrosine phenolic hydroxyl groups in the CPP, converting them into free radical forms, which are then grafted with ε-PLL chloride to form esters. In this process, the low-temperature reaction effectively prevents the ε-PLL chloride from forming amides with its own amino groups. In this way, the cotton fabric can rely on the ε-PLL on the surface to absorb moisture, increase its thermal conductivity to obtain a cool feeling, and at the same time achieve Ag + The dual bactericidal effect of ε-PLL improves the antibacterial properties of cotton fabrics. DETAILED DESCRIPTION

[0017] The present invention can be better understood according to the following examples. However, it is easy for those skilled in the art to understand that the contents described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

[0018] Example 1

[0019] A method for cool antibacterial finishing of cotton fabrics, comprising the following steps:

[0020] 1. Immerse the cotton fabric in 105g / L sodium periodate solution with a pH value of 2.0, with a bath ratio of 40:1, react at 35°C for 5h, then wash and dry;

[0021] 2. The cotton fabric prepared in step 1 was immersed in an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate containing 4-sulfonylcalixa[6]arene, CPP and biotin silver nanoparticles with an average particle size of 20 nm, with the dosage of 150 mg / m 2 Cotton fabric, 6g / m 2 Cotton fabric and 450mg / m 2 Cotton fabric, reflux reaction at 75℃ for 6h, washed and dried;

[0022] 3. Soak the cotton fabric in step 2 in pyridine containing ε-PLL with a weight average molecular weight of 4000 and trichlorotriazine at 350 μW / cm 2 Triethylamine was added dropwise under ultraviolet irradiation while stirring. The dosage of ε-PLL, trichlorotriazine and triethylamine was 18 g / m 2 Cotton fabric, 1.53g / m 2 Cotton fabric and 0.84g / m 2 For cotton fabric, react at -5℃ for 7 minutes, then wash and dry.

[0023] Example 2

[0024] A method for cool antibacterial finishing of cotton fabrics, comprising the following steps:

[0025] 1. Immerse the cotton fabric in 120g / L sodium periodate solution with a pH value of 1.0, with a bath ratio of 50:1, react at 30°C for 6h, then wash and dry;

[0026] 2. Soak the cotton fabric in step 1 in an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate containing calix[6]arene, CPP and biotin silver nanoparticles with an average particle size of 5 nm, with the dosage of 80 mg / m 2 Cotton fabric, 8g / m 2 Cotton fabric and 300mg / m 2 Cotton fabric, reflux reaction at 60℃ for 8h, washed and dried;

[0027] 3. Soak the cotton fabric in step 2 in pyridine containing ε-PLL with a weight average molecular weight of 3600 and trichlorotriazine at 400 μW / cm 2 Triethylamine was added dropwise under ultraviolet irradiation while stirring. The dosage of ε-PLL, trichlorotriazine and triethylamine was 10 g / m 2 Cotton fabric, 1.84g / m 2 Cotton fabric and 0.50g / m 2 For cotton fabric, react at -10℃ for 5 minutes, then wash and dry.

[0028] Example 3

[0029] A method for cool antibacterial finishing of cotton fabrics, comprising the following steps:

[0030] 1. Immerse the cotton fabric in 100 g / L sodium periodate solution with a pH value of 2.5, with a bath ratio of 30:1, react at 40°C for 3 hours, then wash and dry;

[0031] 2. Soak the cotton fabric in step 1 in an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate containing 4-tert-butylcalix[6]arene, CPP and biotin silver nanoparticles with an average particle size of 100 nm, with the dosage of 200 mg / m 2 Cotton fabric, 5g / m 2 Cotton fabric and 500mg / m 2 Cotton fabric, reflux reaction at 85℃ for 5h, washed and dried;

[0032] 3. Soak the cotton fabric in step 2 in pyridine containing ε-PLL with a weight average molecular weight of 4300 and trichlorotriazine at 250 μW / cm 2 Triethylamine was added dropwise under ultraviolet irradiation while stirring. The dosage of ε-PLL, trichlorotriazine and triethylamine was 20 g / m 2 Cotton fabric, 0.92g / m 2 Cotton fabric and 1.01g / m 2 For cotton fabric, react at 4℃ for 10 minutes, then wash and dry.

[0033] Comparative Example 1 (without biotin nanosilver)

[0034] 1. Immerse the cotton fabric in 105g / L sodium periodate solution with a pH value of 2.0, with a bath ratio of 40:1, react at 35°C for 5h, then wash and dry;

[0035] 2. Soak the cotton fabric in step 1 in an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate containing 4-sulfonylcalixa[6]arene and CPP, with the dosage of 150 mg / m 2 Cotton fabric and 6g / m 2 Cotton fabric, reflux reaction at 75℃ for 6h, washed and dried;

[0036] 3. Soak the cotton fabric in step 2 in pyridine containing ε-PLL with a weight average molecular weight of 4000 and trichlorotriazine at 350 μW / cm 2 Triethylamine was added dropwise under ultraviolet irradiation while stirring. The dosage of ε-PLL, trichlorotriazine and triethylamine was 18 g / m 2 Cotton fabric, 1.53g / m 2 Cotton fabric and 0.84g / m 2 For cotton fabric, react at -5℃ for 7 minutes, then wash and dry.

[0037] Comparative Example 2 (without calixarene)

[0038] 1. Immerse the cotton fabric in 105g / L sodium periodate solution with a pH value of 2.0, with a bath ratio of 40:1, react at 35°C for 5h, then wash and dry;

[0039] 2. Soak the cotton fabric in step 1 in an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate containing CPP and biotin silver nanoparticles with an average particle size of 20 nm, with the dosage of 6 g / m 2 Cotton fabric and 450mg / m 2 Cotton fabric, reflux reaction at 75℃ for 6h, washed and dried;

[0040] 3. Soak the cotton fabric in step 2 in pyridine containing ε-PLL with a weight average molecular weight of 4000 and trichlorotriazine at 350 μW / cm 2 Triethylamine was added dropwise under ultraviolet irradiation while stirring. The dosage of ε-PLL, trichlorotriazine and triethylamine was 18 g / m 2 Cotton fabric, 1.53g / m 2 Cotton fabric and 0.84g / m 2 For cotton fabric, react at -5℃ for 7 minutes, then wash and dry.

[0041] Comparative Example 3 (without UV irradiation)

[0042] 1. Immerse the cotton fabric in 105g / L sodium periodate solution with a pH value of 2.0, with a bath ratio of 40:1, react at 35°C for 5h, then wash and dry;

[0043] 2. The cotton fabric prepared in step 1 was immersed in an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate containing 4-sulfonylcalixa[6]arene, CPP and biotin silver nanoparticles with an average particle size of 20 nm, with the dosage of 150 mg / m 2 Cotton fabric, 6g / m 2 Cotton fabric and 450mg / m 2 Cotton fabric, reflux reaction at 75℃ for 6h, washed and dried;

[0044] 3. Soak the cotton fabric in step 2 in pyridine containing ε-PLL with a weight average molecular weight of 4000 and trichloro-s-triazine, and drip triethylamine while stirring. The amounts of ε-PLL, trichloro-s-triazine and triethylamine are 18 g / m 2 Cotton fabric, 1.53g / m 2 Cotton fabric and 0.84g / m 2 For cotton fabric, react at -5℃ for 7 minutes, then wash and dry.

[0045] Antimicrobial Testing Methods

[0046] The antibacterial effects of the cotton fabrics treated by the methods of Examples 1-3 and Comparative Examples 1-3 on Staphylococcus aureus, Pseudomonas aeruginosa and Candida albicans were tested using the AATCC100-2004 standard. The results are shown in Table 1.

[0047] Table 1

[0048]

[0049] From the data in Table 1, it can be seen that compared with the comparative example, the cotton fabric treated by the method of the present invention has better antibacterial and bactericidal properties against Gram-positive bacteria, Gram-negative bacteria and fungi, which is mainly due to the coordination of Ag + and ε-PLL, and Ag + Bound by coordination bonds, it will not produce antagonistic effects with ε-PLL, but will instead transform into superposition and synergy. Comparative Example 1 does not add biotin nanosilver particles to the finishing process, and it also cannot catalyze the formation of Schiff base and cannot obtain the later antibacterial effect; the finishing method of Comparative Example 2 does not add a phase transfer catalyst, calixarene, and there are obstacles in the contact reaction between cotton fabric and CPP, which requires a phase transfer catalyst. In addition, CPP is a peptide with a certain structure and polarity, and calixarene has a cavity that can effectively carry CPP molecules. Therefore, the lack of calixarene causes CPP to be unable to bind to cotton fabrics, let alone ε-PLL, so it can only rely on trace amounts of Ag. + A limited antibacterial effect is obtained; in comparative example 3, in the absence of ultraviolet irradiation, the phenolic hydroxyl group of the tyrosine residue on CPP cannot be activated as a free radical, and cannot preferentially undergo esterification with ε-PLL chloride, resulting in amidation between or within the ε-PLL chloride molecules, and loss of grafting activity. Most of the ε-PLL can only rely on electrostatic adsorption to bind to the cotton fabric, and its antibacterial effect will also be significantly reduced.

[0050] Contact Coolness Coefficient Determination

[0051] According to GB-T 35263-2017 “Testing and evaluating the instantaneous coolness of textiles upon contact”, the contact coolness coefficient of the cotton fabrics before and after finishing by the methods of Examples 1-3 and Comparative Examples 1-3 was measured using the FFZ413-II Textile Instant Coolness Tester. The results are shown in Table 2.

[0052] Table 2

[0053] Before finishing Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 <![CDATA[q max (J / (cm 2 ·s))]]> 0.13 0.32 0.29 0.28 0.17 0.18 0.20

[0054] As shown in Table 2, the contact coolness coefficient of cotton fabrics treated according to the methods of Examples 1-3 is significantly improved, reaching above 0.25. According to the grades of FZ / T62042 "Cool Fabric Bedding", the product of Example 1 has reached AAA grade, and the products of Examples 2 and 3 have also reached AA grade.+ , Comparative Example 2 has no calixarene, cannot form the Schiff base of CPP-cotton fabric, cannot bind ε-PLL, and cannot improve hygroscopicity; Comparative Example 3 has no phenolic hydroxyl group of activated tyrosine, cannot bind ε-PLL, cannot improve hygroscopicity, and cannot retain water and moisture. Comparative Examples 1-3 cannot complete the grafting reaction and cannot repair the gaps and burrs on the surface of cotton fibers. Taken together, the above reasons lead to the fact that the cotton fabric after finishing feels less cool to the touch than the cotton fabric in the embodiment.

[0055] The present invention provides a method and idea for a cool antibacterial finishing method for cotton fabrics. There are many methods and ways to implement the technical solution. The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the protection scope of the present invention. All components not specified in this embodiment can be implemented by existing technologies.

[0056] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for cool antibacterial finishing of cotton fabric, characterized in that: The steps include: S1. The cotton fabric is immersed in a sodium periodate solution for reaction, and then washed and dried; S2. soaking the cotton fabric obtained in step S1 in an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate containing calixarene, CPP and biotin silver nanoparticles, reflux reaction, washing with water and drying; the calixarene is one of calix[6]arene, 4-tert-butylcalix[6]arene and 4-sulfonylcalix[6]arene; S3. The cotton fabric obtained in step S2 is immersed in pyridine containing ε-PLL and trichloro-s-triazine, and triethylamine is added dropwise under ultraviolet irradiation while stirring. After the reaction, the fabric is washed with water and dried.

2. The method for cool antibacterial finishing of cotton fabric according to claim 1, characterized in that: In step S1, the concentration of the sodium periodate solution is 100-120 g / L, and the pH value is 1.0-2.

5.

3. The method for cool antibacterial finishing of cotton fabric according to claim 1, characterized in that: In step S1, the bath ratio of the immersion is 30:1-50:1, the temperature is 30-40°C, and the time is 3-6h.

4. The method for cool antibacterial finishing of cotton fabric according to claim 1, characterized in that: In step S2, the average particle size of the biotin silver nanoparticles is 5-100 nm.

5. The method for cool antibacterial finishing of cotton fabric according to claim 1, characterized in that: In step S2, the dosage of calixarene, CPP and biotin silver nanoparticles is 80-200 mg / m 2 Cotton fabric, 5-8g / m 2 Cotton fabric and 300-500mg / m 2 Cotton fabric.

6. The method for cool antibacterial finishing of cotton fabric according to claim 1, characterized in that: In step S2, the reflux reaction temperature is 60-85°C and the time is 5-8h.

7. The method for cool antibacterial finishing of cotton fabric according to claim 1, characterized in that: In step S3, the amount of ε-PLL, trichlorotriazine and triethylamine is 10-20 g / m 2 Cotton fabric, 0.92-1.84g / m 2 Cotton fabric and 0.50-1.01g / m 2 Cotton fabric.

8. The method for cool antibacterial finishing of cotton fabric according to claim 1, characterized in that: In step S3, the ε-PLL weight average molecular weight is 3600-4300, and the ultraviolet irradiation intensity is 250-400 μW / cm 2 .

9. The method for cool antibacterial finishing of cotton fabric according to claim 1, characterized in that: In step S3, the reaction temperature is -10-4°C and the reaction time is 5-10 min.

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