WO2016192388A1

WO2016192388A1 - Method for finishing fabric by adopting mosquito repelling microcapsules

Info

Publication number: WO2016192388A1
Application number: PCT/CN2015/099447
Authority: WO
Inventors: 周琪
Original assignee: 常州市金坛翰广科技有限公司
Priority date: 2015-06-04
Filing date: 2015-12-29
Publication date: 2016-12-08
Also published as: CN104878607B; CN104878607A

Abstract

The present invention relates to the field of after-finishing of textile, and particularly relates to a method suitable for durable mosquito-repelling finishing on fabric. The method comprises: first preparing a maleic anhydride grafted polypropylene raw material, then preparing the raw material into spinning yarn by using a melt spinning technology; finishing mosquito repelling microcapsules on the spinning yarn; finally coating a polytetrafluoroethylene coating layer having a micropore structure on finished polypropylene fiber spinning yarn, thus obtaining polypropylene fiber finished and modified by using the mosquito repelling microcapsules; and weaving the finished and modified polypropylene fiber into fabric. By coating a tetrafluoroethylene protection layer outside finished polypropylene fiber, microcapsules can be tightly sandwiched, thereby preventing more effectively the microcapsules from falling off.

Description

Method for finishing fabric by using mosquito repellent microcapsule

Technical field

The invention belongs to the field of textile finishing, and in particular relates to a method suitable for durable mosquito repellent finishing of fabrics.

Background technique

Summer is a season with frequent mosquitoes. After being bitten by mosquitoes, it is difficult to resist, and mosquitoes transmit diseases through blood sucking by hedgehogs. Even if they do not transmit diseases, they cause serious harassment and cause skin diseases.

Mosquito repellent plays a major role in the prevention and control of medical insects. Long-term use of mosquito-repellent mosquito repellent is prone to cause adverse reactions such as cough and chest tightness, especially for children, allergies, and asthma. The cosmetics with mosquito repellent effect are mainly chemically synthesized repellents such as DEET. DEET), insect repellent oil (DMP) or citronellal, etc., are applied to the skin to form a protective film so that the mosquito does not dare to approach. However, this chemically added repellent may cause skin irritation.

In recent years, there have been reports on the use of plant extracts as mosquito repellents for human body, for example, using lemon eucalyptus extract, citronella oil, geranium oil, lavender oil, rosemary oil, clove oil, cedar oil, and the like. However, the mosquito repellent containing the volatile oil of the plant as a main component has a short action time, generally 1 to 2 hours.

As one of the three elements of clothing, fabric fabric is the most important factor in determining the function of clothing. The mosquito repellent finishing of fabrics has broad commercial prospects, but it is also a major challenge in the field of textile chemistry and engineering. The micro-capsule technology can be used to organize the mosquito repellent material onto the fabric, so that the mosquito repellent material can be slowly released. However, there is a problem that the fabric and the functional microcapsule have poor adhesion, which greatly affects the performance of the mosquito repellent fabric.

Summary of the invention

The technical problem to be solved by the present invention is that in the prior art, the fastness of the mosquito repellent microcapsules to the fabric is low, which affects the long-lasting use of the mosquito repellent fabric.

In order to solve this technical problem, the technical solution adopted by the present invention is:

Providing a method for finishing a fabric by using a mosquito repellent microcapsule: firstly preparing a polypropylene raw material grafted with maleic anhydride, and then preparing the raw material into a spinning by a melt spinning process, and arranging the mosquito repellent microcapsule to On the spinning, finally, the polytetrafluoroethylene coating with microporous structure is coated on the polypropylene fiber after finishing, and the polypropylene fiber which is modified by the mosquito repellent microcapsule is obtained, and the modified polypropylene spinning is finished. The silk is woven into a fabric, and the fabric has a long-lasting mosquito repellent effect.

The specific steps are:

(1) Preparation of polypropylene raw material grafted with maleic anhydride

Add polypropylene and xylene to a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, stir to a temperature of 110-115 ° C, then add maleic anhydride, continue stirring until the material is completely dissolved; To 120-125 ° C, a solution of benzoyl peroxide in xylene was added dropwise to the system. After the addition was completed, the system was heated to 128-132 ° C. After stirring for 3-4 hours, the temperature of the system was lowered. To 45-55 ° C, and add acetone to the system to precipitate the product,

The product obtained above is subjected to suction filtration, washing, placed in a Soxhlet extractor, extracted with acetone for 24 hours, and then dried at 75-80 ° C to obtain maleic anhydride-grafted polypropylene.

After grafting maleic anhydride onto the raw material polypropylene, the polarity of the raw material is enhanced, and the spinning prepared by using the polar polypropylene raw material can be better combined with the repellent microcapsules. More importantly: it can attract and promote the close coating of the polar polypropylene fiber by the subsequent Teflon coating, and avoid the coating layer falling off during washing, rubbing, etc.

Among them, polypropylene is Blue Star Group Tianjin Petrochemical 3# special polypropylene, melt index 4.5～6.0g/10min,

The mass of the added maleic anhydride is 8-10% of the mass of the polypropylene, the amount of the added benzoyl peroxide is 3-5% of the mass of the polypropylene, and the dropwise addition of the xylene solution of the benzoyl peroxide is added dropwise. The time is 30-40 minutes, the mass ratio of total xylene to polypropylene added to the system is 2 - 2.3:1;

(2) Preparation of modified polypropylene spinning

The maleic anhydride grafted polypropylene prepared in the step (1) is pulverized, melt-extruded by a screw of a plastic wire drawing machine, and extruded through a spinning hole on a spinning casing to form a filament flow, thereby obtaining a modified Polypropylene spinning,

In this step, the maleic anhydride grafted polypropylene is pulverized to 200-250 mesh, and then put into a plastic spinning machine through a screw melt extrusion to form a fluid into the screw end filter to perform the first-stage spinning filtration. Further removing the larger diameter impurity particles in the material, and then measuring the pressure by the metering pump, uniformly pressurizing the fluid into the spinning box equipped with the assembly, and the filter screen on the spinneret in the box is pressurized and constant pressure, and Further filtering, the spinning orifice is evenly arranged on the spinning plate, and the fluid is extruded into a filament flow. The filament flow is cooled by the side of the tunnel of the spinning box to form a fiber, and the primary fiber is naturally drawn down in the tunnel to obtain Modified polypropylene spinning,

The temperature of each screw of the wire drawing machine is set to: one zone 190 ° C, two zones 240 ° C, three zones 250 ° C, four zones 250 ° C, five zones 245 ° C, flange zone 240 ° C, box 230 ° C; The diameter of the spinneret is 0.7 mm;

(3) Repellent microcapsule finishing of modified polypropylene spinning

The modified polypropylene spun obtained in the step (2) is dipped and dried by using the finishing liquid of the mosquito repellent microcapsule, and the modified polypropylene spun yarn having the mosquito repellent microcapsules is obtained.

Wherein, the dipping operation is two dip and two rolling, the bath ratio (spinning fiber weight: finishing liquid weight) is 1:25, the rolling residual ratio is 70%-80%, and the drying is performed at 70 ° C after dipping.

The mosquito repellent microcapsule is prepared by using the plant extract with mosquito repellent effect as the core material, and the material of the capsule wall is preferably a natural organic polymer material, and of course, it can also be a common microcapsule wall material, and the particle size of the microcapsule is controlled to 1 to 10 microns,

Preferably, the core material plant extract is selected from one or both of azadirachtin, geranium extract, menthyl lactate, honeysuckle extract, wild chrysanthemum extract, musk extract, atractylodes extract or clove extract. The above mixture,

The concentration of the microcapsules in the finishing liquid of the above mosquito repellent microcapsules is 15-30 g/L;

(4) coated polytetrafluoroethylene protective layer

The modified polypropylene spun which is obtained by the step (3) and is provided with the mosquito-repellent microcapsules is immersed in a system composed of tetrafluoroethylene monomer, deionized water, activator, initiator, softener and porogen. After the dipped polypropylene fiber is dried at 80 ° C, and heat treated at 120 ° C for 5-15 minutes, a polytetrafluoroethylene coated finishing modified polypropylene spinning having a microporous structure is obtained.

Wherein, the mass ratio of the modified polypropylene spinning to the tetrafluoroethylene monomer is 10:1 to 1.5, and the ratio of the modified polypropylene spinning to the deionized water is 1-2:10 g/mL, the activator The mass ratio of the initiator, the softener, the porogen and the deionized water are respectively 0.3-0.5%, 0.6-1.2%, 0.4-1.0%, 0.2-0.4%,

The activator is HCl, the initiator is ammonium persulfate or potassium persulfate, the softener is hydroxy silicone emulsion or amino silicone emulsion, and the porogen is PVP (PVPK17 produced by Hangzhou Luke Technology Development Co., Ltd.) , porogen PVPK30);

(5) The finished modified polypropylene spun which is coated with the protective layer of polytetrafluoroethylene obtained in the step (4) is woven into a fabric, and the fabric has a long-lasting mosquito repellent effect.

The invention has the beneficial effects that: the microcapsules having the mosquito repellent effect are arranged on the surface of the modified polypropylene spun yarn, and then the outer surface of the polypropylene spun yarn is coated with a protective layer of tetrafluoroethylene, which is finished. The microcapsules are tightly sandwiched and controlled between the polypropylene spun yarn and the tetrafluoroethylene coating layer by means of mechanical wrapping; while some of the prior art binders are used to bond the microcapsules to the spinning, for a long time. The bonding material is easily degraded, broken, and thus ineffective, and the fixing method in the present invention can more effectively prevent the falling off of the microcapsules by comprehensively wrapping.

Secondly, the protective layer of tetrafluoroethylene coated with polypropylene has a microporous structure, and the mosquito repellent effective substance in the microcapsule can be released through the micropores; however, it is necessary to control the micropore size to be smaller than the particle size of the microcapsule to avoid microcapsules. Sliding out through the micropores.

detailed description

In the following examples, the preparation process of the mosquito repellent microcapsules in the comparative examples is as follows:

60mL of 0.6g / L gelatin and 0.6g / L gum arabic were mixed at a constant temperature of 40 ° C, and 20 mL of menthyl lactate was added. For 12g/L ethanol solution, 10,000r/min for 4min to obtain a dispersion emulsion, adjust the pH=4.0 with 100g/L acetic acid aqueous solution, cool the ice water to 5°C, adjust the pH=9.0 with 100g/L sodium hydroxide solution, add The 370 g/L aqueous formaldehyde solution was solidified, and the temperature was raised to 40 ° C to obtain a mosquito repellent microcapsule having a particle diameter of 4 to 8 μm.

Example 1

(1) Preparation of raw materials, adding polypropylene and xylene to a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, stirring to a temperature of 112 ° C, adding maleic anhydride, and continuing to stir until the material is completely dissolved; The temperature of the obtained system was raised to 120 ° C, and a xylene solution of benzoyl peroxide was added dropwise to the system. After the addition was completed, the obtained system was heated to 130 ° C, and after stirring for 4 hours, the temperature of the system was lowered. At 50 ° C, acetone was added to the system to precipitate the product.

The product obtained above was subjected to suction filtration, washed, placed in a Soxhlet extractor, extracted with acetone for 24 hours, and dried at 80 ° C to obtain maleic anhydride-grafted polypropylene.

Among them, polypropylene is Blue Star Group Tianjin Petrochemical 3# special polypropylene, melting index 5.8g/10min,

The mass of the added maleic anhydride is 10% of the mass of the polypropylene, the amount of the added benzoyl peroxide is 3.5% of the mass of the polypropylene, and the dropwise addition time of the xylene solution of the benzoyl peroxide is 30 minutes. The mass ratio of total xylene to polypropylene added to the system is 2:1;

(2) The maleic anhydride-grafted polypropylene prepared in the step (1) is pulverized, melt-squeezed by a screw of a plastic wire drawing machine, and extruded through a spinning hole on a spinning casing to form a filament flow. Modified polypropylene spinning,

Wherein, the temperature of each section of the screw of the spinning machine is set, one zone 190 ° C, two zones 240 ° C, three zones 250 ° C, four zones 250 ° C, five zones 245 ° C, flange zone 240 ° C, box 230 ° C; The diameter of the spinneret is 0.7mm;

(3) using the finishing liquid of the above-mentioned mosquito repellent microcapsules, the modified polypropylene spun yarn obtained in the step (2) is dipped and dried to obtain a modified polypropylene spun yarn in which the mosquito repellent microcapsules are arranged.

Among them, the concentration of the microcapsules in the finishing liquid of the mosquito repellent microcapsules is 25 g/L.

The dipping operation is two-dip two-rolling, the bath ratio (spinning fiber weight: finishing liquid weight) is 1:25, the rolling residual ratio is 75%, and drying is performed at 70 ° C after dipping;

(4) coating the protective layer of polytetrafluoroethylene, and spinning the modified polypropylene obtained by the step (3) with the mosquito-repellent microcapsules, immersed in tetrafluoroethylene monomer, deionized water, activator HCl, Soaking in a system consisting of potassium persulfate, softener hydroxy silicone emulsion and porogen PVPK17, the rolling ratio is 80%, and the spun polypropylene is dried at 80 ° C and dried at 120 ° C. After heat treatment for 15 minutes, a polytetrafluoroethylene-coated finishing modified polypropylene spinning having a microporous structure is obtained.

Wherein, the mass ratio of the modified polypropylene spinning to the tetrafluoroethylene monomer is 10:1.2, and the ratio of the modified polypropylene spinning to the deionized water is 2:10 g/mL, activator, initiator, softener The mass ratio of porogen to deionized water is 0.4%, respectively. 1.0%, 0.5%, 0.2%;

(5) The finishing modified polypropylene obtained by coating the polytetrafluoroethylene protective layer obtained in the step (4) is woven into a woven fabric.

The prepared fabric was immediately washed with water, and the content of the active ingredient of the mosquito repellent on the fabric before and after the washing was as shown in Table 1.

Example 2

(1) Preparation of raw materials, adding polypropylene and xylene to a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, stirring and heating to 115 ° C, adding maleic anhydride, and continuing to stir until the materials are completely dissolved; The temperature of the obtained system was raised to 125 ° C, and a xylene solution of benzoyl peroxide was added dropwise to the system. After the addition was completed, the obtained system was heated to 130 ° C, and after stirring for 3 hours, the temperature of the system was lowered. At 50 ° C, acetone was added to the system to precipitate the product.

Among them, polypropylene is Blue Star Group Tianjin Petrochemical 3# special polypropylene, melting index 5.0g/10min,

The mass of maleic anhydride added is 9% by mass of polypropylene, the amount of benzoyl peroxide added is 4% by mass of polypropylene, and the dropping time of xylene solution dropwise added with benzoyl peroxide is 40 minutes. , the mass ratio of total xylene to polypropylene added to the system is 2.1:1;

(4) coating the protective layer of polytetrafluoroethylene, and spinning the modified polypropylene obtained by the step (3) with the mosquito-repellent microcapsules, immersed in tetrafluoroethylene monomer, deionized water, activator HCl, Fully immersed in the system consisting of ammonium persulfate, softener amino silicone emulsion and porogen PVPK17. The spun polypropylene was dried at 80 ° C and heat treated at 120 ° C for 15 min to obtain Microporous structure of polytetrafluoroethylene coated finishing modified polypropylene spinning,

Wherein, the mass ratio of the modified polypropylene spinning to the tetrafluoroethylene monomer is 10:1.5, and the ratio of the modified polypropylene spinning to the deionized water is 1.5:10 g/mL, activator, initiator, softener The mass ratio of porogen to deionized water is 0.3%, 1.0%, 0.5%, 0.4%;

Comparative example 1:

Compared with the first embodiment, the protective layer of the polytetrafluoroethylene is not coated, and the remaining steps are the same as those of the first embodiment. The specific steps are as follows:

(4) The finishing modified polypropylene obtained in the step (3) is woven into a woven fabric.

Comparative example 2:

The polypropylene in the raw material was not grafted with maleic anhydride as compared with Example 1, and the remaining steps were the same as in Example 1.

Table 1 shows the changes in the content of active components of mosquito repellent on the modified polypropylene spun fabric coated with the protective layer of polytetrafluoroethylene before and after washing in each of the examples and comparative examples:

Table 1

Mosquito repellent performance test:

300 mosquitoes were placed in a mosquito cage with a length × width × height of 40 cm × 30 cm × 30 cm, and the modified finishing fabric prepared in the above Example 1 was cut into an area of 4 cm × 4 cm, and placed in a mosquito cage for 2 minutes. Observe and record the number of mosquitoes staying on the fabric; remove the fabric (make sure that no mosquitoes are taken out), wash it once according to GB/T8629-2001, dry it and put it into the mosquito cage. Observe and record the stay at 2 minutes. The number of mosquitoes on the fabric; the removal was also washed, dried and tested according to GB/T8629-2001, and recorded a total of 3 times.

The same experiment was also carried out on the fabrics of Example 2 and Comparative Examples 1 and 2, and the results are shown in Table 2:

Table 2

	1次1 time	洗涤1次Wash once	洗涤2次Wash 2 times
实施例1Example 1	0只0 only	0只0 only	2只2
实施例2Example 2	0只0 only	0只0 only	0只0 only
对比实施例1Comparative Example 1	0只0 only	24只24	45只45
对比实施例2Comparative Example 2	0只0 only	17只17	29只29

Claims

The invention relates to a method for finishing a fabric by using a mosquito repellent microcapsule, which is characterized in that: firstly, a polypropylene raw material grafted with maleic anhydride is prepared, and then the raw material is prepared into a spinning by a melt spinning process. Silk, the mosquito repellent microcapsules are arranged on the spinning, and finally the polytetrafluoroethylene coating with microporous structure is coated on the spun polypropylene fiber to obtain the polypropylene fiber after the mosquito repellent microcapsule finishing modification. , the modified polypropylene spun yarn is woven into a fabric.
The arranging method according to claim 1, wherein the specific step of the method is

(1) Preparation of polypropylene raw material grafted with maleic anhydride

Add polypropylene and xylene to a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, stir to a temperature of 110-115 ° C, then add maleic anhydride, continue stirring until the material is completely dissolved; To 120-125 ° C, a solution of benzoyl peroxide in xylene was added dropwise to the system. After the addition was completed, the system was heated to 128-132 ° C. After stirring for 3-4 hours, the temperature of the system was lowered. To 45-55 ° C, and add acetone to the system to precipitate the product,

The product obtained above is subjected to suction filtration, washing, placed in a Soxhlet extractor, extracted with acetone for 24 hours, and then dried at 75-80 ° C to obtain maleic anhydride grafted polypropylene;

(2) Preparation of modified polypropylene spinning

The maleic anhydride grafted polypropylene prepared in the step (1) is pulverized, melt-extruded by a screw of a plastic wire drawing machine, and extruded through a spinning hole on a spinning casing to form a filament flow, thereby obtaining a modified Polypropylene spinning;

(3) Repellent microcapsule finishing of modified polypropylene spinning

The modified polypropylene spun obtained in the step (2) is dipped and dried by using a finishing liquid of the mosquito repellent microcapsule to obtain a modified polypropylene spun which is prepared with the mosquito repellent microcapsule;

(4) coated polytetrafluoroethylene protective layer

The modified polypropylene spun which is obtained by the step (3) and is provided with the mosquito-repellent microcapsules is immersed in a system composed of tetrafluoroethylene monomer, deionized water, activator, initiator, softener and porogen. After the dipped polypropylene fiber is dried at 80 ° C, and heat treated at 120 ° C for 5-15 minutes, a polytetrafluoroethylene coated finishing modified polypropylene spinning having a microporous structure is obtained;

(5) The finishing modified polypropylene obtained by coating the polytetrafluoroethylene protective layer obtained in the step (4) is woven into a woven fabric.
The finishing method according to claim 2, wherein the polypropylene in the step (1) is a special polypropylene of the Blue Star Group Tianjin Petrochemical Company 3, and has a melt index of 4.5 to 6.0 g/10 min.
The finishing method according to claim 2, wherein in the step (1), the mass of the maleic anhydride added is 8 to 10% by mass of the polypropylene, and the amount of the benzoyl peroxide added is the mass of the polypropylene. 3-5%, the dropwise addition time of the xylene solution of benzoyl peroxide added is 30-40 minutes, and the mass ratio of total xylene to polypropylene added to the system is 2-2.3:1.
The finishing method according to claim 2, wherein in the step (2), the maleic anhydride grafted polypropylene is pulverized to 200-250 mesh, and then put into a plastic spinning machine to be melt-squeezed by a screw to form a fluid. Enter the screw end filter to carry out the first-stage spinning filter to further remove the larger diameter particles in the material, and then pressurize the metering pump to uniformly press the fluid into the spinning box with the components in the box. The screen filter on the spinneret is pressurized and constant pressure, and further filtering is performed. The spinneret is evenly arranged on the spinneret to extrude the fluid into a filament flow, and the filament flow passes through the side of the spine of the spinning box. Cooling into fiber, the primary fiber is naturally drawn down in the tunnel, and the modified polypropylene is spun.

The temperature of each screw of the wire drawing machine is set to 190 ° C in one zone, 240 ° C in two zones, 250 ° C in three zones, 250 ° C in four zones, 245 ° C in five zones, 240 ° C in flange zone, 230 ° C in box zone; The spinneret hole diameter is 0.7 mm.
The finishing method according to claim 2, wherein the core material of the mosquito repellent microcapsule according to the step (3) is a plant extract having a mosquito repellent effect, and the material of the capsule wall is a natural organic polymer material. The size of the mosquito repellent microcapsules is 1 to 10 micrometers.
The finishing method according to claim 6, wherein the plant extract is azadirachtin, geranium extract, menthyl lactate, honeysuckle extract, wild chrysanthemum extract, musk extract, and atractylodes extract. Or one or a mixture of two or more of clove extracts.
The finishing method according to claim 2, wherein the immersing operation in the step (3) is two-dip two-rolling, the bath ratio is 1:25, the rolling ratio is 70%-80%, and after the immersion Dry at 70 °C.
The finishing method according to claim 2, wherein in step (4), the mass ratio of the modified polypropylene spinning and the tetrafluoroethylene monomer assembled with the mosquito repellent microcapsules is 10:1 to 1.5, and the finishing has The ratio of modified polypropylene spinning to deionized water of mosquito repellent microcapsules is 1-2:10g/mL, and the mass ratio of activator, initiator, softener, porogen and deionized water is 0.3-0.5 respectively. %, 0.6-1.2%, 0.4-1.0%, 0.2-0.4%.