WO2020113903A1 - Skincare and antibacterial microcapsule finishing agent, and preparation method therefor and application thereof - Google Patents

Abstract

Disclosed are a skincare and antibacterial microcapsule finishing agent, and a preparation method therefor and application thereof. The finishing agent comprises an organosilicon microcapsule; the surface of the organosilicon microcapsule is modified by using an organosilicon quaternary ammonium salt; in the organosilicon microcapsule, an aloe extraction liquid and squalene are used as core materials, and tetraethylorthosilicate wall material. A non-adhesive skincare and antibacterial microcapsule finishing agent is obtained by first preparing the organosilicon microcapsule by means of a sol-gel method, and then using the organosilicon quaternary ammonium salt to modify the prepared microcapsule. When in use, the finishing agent is directly added into a cellulose fiber fabric post-finishing liquid, without adding an adhesive; a finished fabric has lasting skincare and moisturizing effects, and also has lasting antibacterial performance; moreover, the touch feel and style of the fabric are not affected.

Description

Skin care antibacterial microcapsule finishing agent, preparation method and application thereof Technical field

The invention belongs to the technical field of fabric finishing, and in particular relates to a skin care and antibacterial microcapsule finishing agent, and a preparation method and application thereof.

Background technique

Close-fitting textiles are a good carrier for skin care and health care. Various skin care and health care products are loaded onto underwear and fabrics through spinning, coating, and post-finishing methods to sustain their effectiveness. The emergence of various health-care functional textiles has increased the value of textiles. CN101418517A Antibacterial sol obtained by using quaternary ammonium salt and TEOS as raw materials under the action of a catalyst, but the antibacterial agent is only adsorbed in the gel network through physical action, and the bacteriostatic rate of E. coli and Staphylococcus aureus after 10 washings are both Less than 80%, the wash resistance is not ideal. CN102704280A discloses a VE microcapsule fabric finishing liquid with skin care function for human skin and a preparation method, using polyurethane as the wall material and VE with moisturizing skin care function as the core material, and using the interfacial polymerization method to obtain the microcapsule emulsion, which is added during finishing After washing the adhesive 10 times, the relative percentage of VE on the fabric reached more than 80%.

In order to solve the problem of bonding between microcapsules and fibers, adhesives such as acrylic and polyurethane are usually used. When the amount of adhesive used is small, because there is no direct affinity between the microcapsules and the fibers, the microcapsules can easily fall off the fabric under the action of friction or washing; if the adhesion of the microcapsules is pursued blindly, the adhesive The amount of use will cause changes in the fabric style, produce a rough feel, or cause the fabric to permeate or even reduce the breathability, reducing the comfort of taking. In recent years, there has also been a textile microcapsule finishing process without binders. CN104746350A uses microcoagulation method to prepare microcapsules containing traditional Chinese medicine oil, and adds them in the in-situ polymerization process of polyacrylate to obtain polyacrylate adhesive containing microcapsules of traditional Chinese medicine oil, no additional adhesive is needed during the finishing process, which endows the fabric The antibacterial properties are resistant to washing, but the essence of the invention still relies on the binder to organize the microcapsules onto the fabric. CNCN108424477A modified the β-cyclodextrin with silane coupling agent KH550, and then included the antibacterial agent limonene to obtain the limonene-KH550 modified β-cyclodextrin inclusion compound, and finally the inclusion compound was combined with gelatin and gum arabic , Limonene, etc. are made into microcapsules. After β-cyclodextrin is modified with silane coupling agent, its silicon hydroxyl group can enhance the curing of microcapsules and the adhesion between microcapsules and fibers, making the capsules more stable and not easy to fall off. Although the microcapsules formed by such natural wall materials have good biocompatibility, they have poor mechanical properties and thermal stability.

Summary of the invention

The purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art, to provide a non-adhesive skin care antimicrobial microcapsule finishing agent, the finishing agent can be directly added to the finishing solution of cellulose fiber fabric during application, without adding viscosity Mixture, in addition to the long-lasting skin care and moisturizing effect, the finished fabric also has long-lasting antibacterial properties, and the feel of the fabric is not affected in any way.

A skin care antimicrobial microcapsule finishing agent, including organosilicon microcapsules and dispersant, the surface of the organosilicon microcapsules is modified with organosilicon quaternary ammonium salt;

The organosilicon microcapsules use aloe extract and squalene as core materials, and ethyl orthosilicate as wall materials.

Further, the mass ratio of the aloe extract and squalene is 1:1-1:2.

Further, the organosilicon quaternary ammonium salt is (trimethoxysilylpropyl) octadecyldimethylammonium chloride or (trimethoxysilylpropyl)tetradecyldimethylammonium chloride .

The preparation method of the skin care antibacterial microcapsule finishing agent includes the following steps:

Step 1: Preparation of core material emulsion: the mixture of aloe extract and squalene is used as an oil phase, mixed with an emulsifier and added to deionized water, and dispersed to obtain an O/W core material emulsion;

Step 2: Prepare wall material solution: add TEOS to deionized water, adjust pH to 2-3, and stir to obtain wall material solution;

Step 3: Prepare organic microcapsules: drop the wall material solution into the O/W core material emulsion, adjust the pH to 8-10, stir, filter, wash and dry to obtain microcapsule solids;

Step 4: Modification of organosilicon quaternary ammonium salt: mix the microcapsule solid and acidic ethanol aqueous solution, add organosilicon quaternary ammonium salt, adjust pH to 8-10, stir, then add dispersant, continue to stir, let stand, that is .

Further, the mass ratio of the oil phase, deionized water and emulsifier in step 1 is 1:50:0.1-1:50:0.3. The emulsifier is one or more of Tween series or Span series.

Further, the concentration of TEOS in step 2 is 10-20wt.%, the stirring rate is 200-300r/min, the stirring temperature is 20-30°C, and the stirring time is 10-30min.

Further, in step 3, the mass ratio of the O/W core material emulsion to the wall material solution is 5-10:1, the drop acceleration rate is 10-30 drops/min, the stirring rate is 400-500r/min, and the stirring temperature is 30 -50℃, stirring time is 3-5h, drying temperature is 60-80℃.

Further, in step 4, the pH of the acidic ethanol aqueous solution is 2-2.5, the ethanol concentration is 15-25% v/v, and the dispersant is one of hydroxymethyl cellulose, sodium polyacrylate or sodium hexametaphosphate.

The application of the skin care antibacterial microcapsule finishing agent in the antibacterial finishing of cellulose fiber fabric.

Further, the above application is specifically to soak the cellulosic fiber fabric in the working fluid, soak and roll one at a time, with a liquid rate of 80%, and then bake at 80-100°C for 10 min, and set at 120-150°C for 40 s. ;

The concentration of the skin care antibacterial microcapsule finishing agent in the working solution is 50-100 g/L, and the pH is 6-7.

Further, the cellulose fiber fabric is a cotton fabric, tencel fabric or modal fabric.

The present invention uses aloe extract and squalene with skin care and moisturizing functions as core materials, TEOS as wall material, sol-gel method to prepare microcapsules, and then modified with organosilicon quaternary ammonium salt to obtain good microcapsules. Heat resistance, and the active groups on the surface of the microcapsules can be covalently combined with the hydroxyl groups on the cellulose fiber, without the need to add a binder when finishing.

Aloe has natural moisturizing and water-locking effects, promotes the degradation of fibrin in the skin, and can reduce the loss of transdermal water; squalene is an important component of human sebum, promotes the repair of aging and damaged cells, and enhances the regeneration of the skin. Has a natural skin care effect.

TEOS can be controlled by adjusting the pH of the system during the hydrolysis and condensation. First, TEOS is partially hydrolyzed. At this time, the molecule contains both alkoxy groups and hydroxyl groups. When added dropwise to the core material emulsion, the TEOS environment As the pH increases, the pre-hydrolyzed TEOS will undergo polycondensation at the O/W interface and gradually deposit on the surface of the core material to form microcapsules.

Adjust the system pH again to completely hydrolyze the remaining unhydrolyzed siloxane on the microcapsules, and then adjust the system pH to alkaline, the fully hydrolyzed microcapsules are cross-linked with the added silicone quaternary ammonium salt to form Si-O-Si The three-dimensional spatial network structure formed by the groups further increases the thermal stability of the microcapsules, and at the same time forms an antibacterial film on the surface of the microcapsules.

The unreacted active groups on the microcapsules can form a strong covalent bond with the hydroxyl groups on the cellulose fiber fabric, which gives the fabric a long-lasting and durable skin care antibacterial function. In addition to the lasting skin care moisturizing effect, the finished fabric It also has long-lasting antibacterial properties, and the feel of the fabric is not affected in any way.

The beneficial effects of the present invention are: 1. Aloe extract and squalene have natural skin care and moisturizing effects, and have no toxic and side effects on the human body. 2. The microcapsules with TEOS as the wall material have good heat resistance and mechanical properties, which can effectively avoid the problem that the microcapsules made of natural polymers as the wall material break the capsule and cause the release of the core material during the high temperature setting process. 3. The heat resistance of the microcapsules modified by silicone quaternary ammonium salt is further improved, and there is no need to add a binder when finishing, and it can form a strong covalent bond with the fabric. 4. The finished fabric has long-lasting and durable skin care and antibacterial functions, and the style of the fabric is not affected after finishing.

detailed description

The present invention will be further described below in conjunction with specific embodiments

Example 1

The preparation of non-adhesive skin care antibacterial microcapsule finishing agent includes the following steps:

(1) Take 5g of aloe extract, 5g of squalene and 1g of Tween-20, respectively, add to 500g of deionized water, ultrasonically stir at 50℃ for 30min to obtain the core material emulsion, control the ultrasonic frequency to 300W, and the stirring rate to 1500r/min ;

(2) Prepare a 20% strength TEOS aqueous solution, adjust the pH to 3 with 2 mol/L hydrochloric acid, and stir at 30°C for 25 min to obtain a wall material hydrolysate with a stirring rate of 300 r/min;

(3) Slowly add 50g of wall material hydrolysate to 500g of core material emulsion, adjust the pH to 9 with 2mol/L NaOH solution, stir at 50°C for 4h, filter and wash, dry at 60°C to obtain white microcapsule solid, drop The acceleration is 20 drops/min and the stirring rate is 500r/min;

(4) Take 10g of microcapsule solid and 30g of acidic ethanol aqueous solution (ethanol content 15%, pH 2), mix at 60℃ for 1h, stirring rate is 800r/min, add 20g (trimethoxysilylpropyl) For octaalkyl dimethyl ammonium chloride, adjust the system pH to 10 with 1 mol/L NaOH, add 0.1 g of sodium polyacrylate dispersant, and continue stirring for 6 h to obtain a non-adhesive skin care antimicrobial microcapsule dispersion.

Take Tencel TS40s*TS40s/133*76 as an example to illustrate the application method:

Prepare 80g/L microcapsule finishing liquid, adjust the pH of the finishing liquid to 6 with citric acid, soak the Tencel fabric in the finishing liquid, one dip and one roll, the liquid rate is 80%, and then bake at 100℃ for 10min , 140 can be shaped for 40s.

Example 2

The preparation of non-adhesive skin care antibacterial microcapsule finishing agent includes the following steps:

(1) Take 4g of aloe extract, 6g of squalene and 1g of Tween-60 respectively, add to 500g of deionized water, ultrasonically stir at 50°C for 40min to obtain the core material emulsion, control the ultrasonic frequency to 400W, and the stirring rate to 1200r/min

(2) Configure a 20% concentration TEOS aqueous solution, adjust the pH to 3 with 1mol/L hydrochloric acid, and stir at 30°C for 25min to obtain a wall material hydrolysate, with a stirring rate of 300r/min;

(3) Slowly add 50g of wall material aqueous solution to 500g of core material emulsion, adjust the pH to 9 with 2mol/L NaOH solution, stir at 50°C for 4h, filter and wash, and dry at 60°C to obtain white microcapsule solid, drop acceleration 20 drops/min, stirring rate 500r/min;

(4) Take 10g of microcapsule solid and 30g of acidic ethanol aqueous solution (ethanol content 15%, pH 2), mix at 60℃ for 1h, stirring rate is 800r/min, add 20g (trimethoxysilylpropyl) Tetraalkyl dimethyl ammonium chloride, adjust the system pH to 10 with 1mol/L NaOH, add 0.2g of sodium polyacrylate dispersant, and continue stirring for 6h to obtain a non-adhesive skin care antimicrobial microcapsule dispersion.

Take cotton C40s*C40s/133*72 as an example to illustrate the application method

Prepare 80g/L microcapsule finishing liquid, adjust the pH of the finishing liquid to 6 with citric acid, soak the cotton fabric in the finishing liquid, soak and roll, the liquid rate is 80%, and then bake at 100℃ for 5min , It can be set at 140℃ for 40s.

Example 3

The preparation of non-adhesive skin care antibacterial microcapsule finishing agent includes the following steps:

(1) Take 5g of aloe extract, 5g of squalene and 1g of Tween-20 respectively, add to 500g of deionized water, ultrasonically stir at 50°C for 30min to obtain the core material emulsion, control the ultrasonic frequency to 400W, and the stirring rate to 1200r/min

(2) Configure a 15% strength TEOS aqueous solution, adjust the pH to 3 with 1mol/L hydrochloric acid, and stir at 30°C for 20min to obtain a wall material hydrolysate, with a stirring rate of 300r/min;

(3) Slowly add 50g of wall material aqueous solution to 400g of core material emulsion, adjust the pH to 9 with 2mol/L NaOH solution, stir at 50°C for 3h, filter and wash, and dry at 60°C to obtain white microcapsule solid, drop acceleration 30 drops/min, stirring rate 500r/min;

(4) Take 10g of microcapsule solid and 50g of acidic ethanol aqueous solution (ethanol content 20%, pH 2.5), mix at 60℃ for 1h, stirring rate is 800r/min, add 20g (trimethoxysilylpropyl) Octane dimethyl ammonium chloride, adjust the system pH to 9.5 with 1mol/L NaOH, add 0.2g hydroxymethyl cellulose dispersant, and continue stirring for 7h to obtain a non-adhesive skin care antimicrobial microcapsule dispersion.

Take Modal M40s*M40s/144*76 as an example to illustrate the application method

Prepare 100g/L microcapsule finishing liquid, adjust the pH of the finishing liquid to 6 with citric acid, soak the modal fabric in the finishing liquid, one dip and one roll, the liquid rate is 80%, and then bake at 100 ℃ for 5min, It can be set at 150℃ for 40s.

Test Example 1

Microcapsule thermal stability

The unmodified and organosilicon quaternary ammonium salt-modified microcapsules in Example 1 were heat-treated under the same conditions, and the core material in the microcapsules was completely released by ultrasonic treatment with n-hexane, and the microcapsules were calculated by liquid chromatography analysis. The amount of change of the core material before and after heat treatment. The results are shown in Table 1:

Table 1

Core material loss rate	Unmodified microcapsules	Modified microcapsules
Vacuum drying at 100℃ for 1h	2.43%	1.17%
Vacuum drying at 100℃ for 2h	5.98%	1.91%

As shown in the above table, the core material loss rate of microcapsules modified by silicone quaternary ammonium salt after heat treatment is significantly reduced, indicating that the thermal stability of the modified microcapsules is further improved.

Test example 2

Simulated home washing experiment: the fabrics finished with non-adhesive fabric skin care and antimicrobial microcapsules were subjected to a simulated home washing experiment to test the number of times of washing resistance. Use a neutral detergent in the domestic washing machine, the bath ratio is 1:30, the water temperature is 40 ℃, after washing for 5 minutes, rinse with clean water once, take out and dry. Follow the above steps to record the number of washing cycles for a washing cycle, retain the corresponding number of samples, and test the moisturizing performance and antibacterial performance.

Moisturizing performance test: Subjects sit for 30 minutes in a constant temperature and humidity room (temperature 20-22°C, relative humidity 50%), take the skin (4cm×4cm) of the symmetrical part inside the left and right arms, and use

The CM 825 skin moisture test probe measures the skin moisture of the sample that is not applied and is recorded as m0 (average 3 times for each test); apply the test sample to the clothing and test the skin moisture every 1, 2, 4, 8h (Take an average of 3 measurements each time), and record mn (n=1, 2, 4, 8), calculate mn-m0, which is the amount of skin moisture change. The results are shown in Table 2:

Table 2

It can be seen from the above table that the skin moisture content of the finished fabric is kept at a relatively high level, and the skin can still maintain a high moisture after 20 washings, indicating that the present invention can impart durable moisturizing properties to the fabric.

Antibacterial performance test: According to FZT73023-2006 "Antibacterial Knitwear", after testing the fabric 20 times after washing, each bacteriostasis value meets the AA level standard, the results are shown in Table 3:

table 3

As can be seen from the above table, the present invention can impart long-term antibacterial properties to fabrics.

Claims (10)

1. A skin care antibacterial microcapsule finishing agent, characterized in that it includes silicone microcapsules, and the surface of the silicone microcapsules is modified with silicone quaternary ammonium salts;

   The organosilicon microcapsules use aloe extract and squalene as core materials, and ethyl orthosilicate as wall materials.
2. The skin care antibacterial microcapsule finishing agent according to claim 1, wherein the mass ratio of the aloe extract and squalene is 1:1-1:2.
3. The skin care antibacterial microcapsule finishing agent according to claim 1, wherein the organosilicon quaternary ammonium salt is (trimethoxysilylpropyl) octadecyl dimethyl ammonium chloride or (trimethoxy) Silylpropyl) tetradecyl dimethyl ammonium chloride.
4. The preparation method of skin care antibacterial microcapsule finishing agent according to claim 1, characterized in that it comprises the following steps:

   Step 1, the mixture of aloe extract and squalene is used as the oil phase, mixed with the emulsifier, added to deionized water, and dispersed to obtain an O/W core material emulsion;

   Step 2: Add TEOS to deionized water, adjust the pH to 2-3, and stir to obtain a wall material solution;

   Step 3: Add the wall material solution to the O/W core material emulsion, adjust the pH to 8-10, stir, filter, wash and dry to obtain microcapsule powder;

   Step 4. Mix the microcapsule powder with the acidic ethanol aqueous solution, add the organosilicon quaternary ammonium salt, adjust the pH to 8-10, stir to modify, then add the dispersant, continue to stir, and let it stand.
5. The preparation method according to claim 4, wherein the mass ratio of the oil phase, deionized water and emulsifier in step 1 is 1:50:0.1-1:50:0.3.
6. The preparation method according to claim 4, characterized in that the concentration of TEOS in step 2 is 10-20wt.%, the stirring rate is 200-300r/min, the stirring temperature is 20-30°C, and the stirring time is 10-30min .
7. The preparation method according to claim 4, wherein the mass ratio of the O/W core material emulsion and the wall material solution in step 3 is 5-10:1, the drop acceleration rate is 10-30 drops/min, and the stirring rate 400-500r/min, stirring temperature 30-50℃, stirring time 3-5h, drying temperature 60-80℃.
8. The preparation method according to claim 4, characterized in that in step 4 the acidic ethanol aqueous solution has a pH of 2-2.5 and an ethanol concentration of 15-25% v/v.
9. The application of the skin care antibacterial microcapsule finishing agent according to claim 1 in the antibacterial finishing of cellulose fiber fabrics, wherein the cellulose fiber fabrics are cotton fabrics, tencel fabrics or modal fabrics.
10. The application according to claim 9, characterized in that: after soaking the cellulose fiber fabric in the working fluid, one dip and one roll, the strip rate is 80%, and then baked at a temperature of 80-100 ℃ for 10min, 120- It can be set at 150℃ for 40s;

    The concentration of the skin care antibacterial microcapsule finishing agent in the working solution is 50-100 g/L, and the pH is 6-7.