Antimosquito finishing agent and preparation method and the application in anti-mosquito cloth
[technical field]
The present invention relates to the function textile field, be specifically related to a kind of antimosquito finishing agent and preparation technology who is used for fabric, and adopt above-mentioned antimosquito finishing agent to prepare the method for anti-mosquito cloth.
[background technology]
Mosquito sucks blood, harasses happy and auspicious work, the living atmosphere except that directly stining thorn, also can propagate multiple serious disease, as malaria, dengue fever (or dengue hemorrhagic fever), Japanese Type-B encephalitis, lymph filariasis, yellow fever, equine encephalitis etc., serious harm human health.According to statistics, there are every year 1000000 people of surpassing to die from mosquito and pass disease.The propagation that the control mosquito passes disease (malaria, dengue fever, Japanese Type-B encephalitis etc.) is the important public hygiene problem of global extensive concern, reduces mosquito and passes disease incidence, alleviates mosquito biography disease burden and has listed the Millennium Development Goals (MDGs) in.Based on this reason, the research activities of universal precaution bite by mosquitos grows with each passing day, and only just has how tame research institution that this difficult problem is studied in the U.S..
The method of outdoor mosquito repellent mainly contains three kinds so far: (1) directly is put on medicaments such as Permethrin, Metadelphene on the skin; (2) spatial repellency; (3) wear mosquito-expelling clothing (or claiming the repellent clothes).But in actual the use, method (1) is not ideal, and medicine volatilizees easily or washed out by sweat, rainwater, and effective acting time is short, and required pharmaceutical quantities is bigger, and mosquito also can see through clothes and bite the skin that is not coated with medicine; Method (2) is that the netted fabric that will flood a certain amount of repellant is suspended in certain space and reaches repellent effect, though this method is effective, the repellent space is little, uses inconvenient; Method (3) is safe, easy to use, is comparatively ideal in recent years mosquito repellent method.
Early stage mosquito-expelling clothing is made with repellant emulsion or solution impregnation clothes, though very effective, not water-fast wash or rainwater dash to drench.In recent years, mosquito-expelling clothing more and more is subjected to common concern both domestic and external as novel functional fabric, and research and development is quite active, and all kinds of mosquito-expelling clothing listings are abroad arranged in succession; Domestic later relatively at this area research, but quite pay attention to, its study on the industrialization classified one of as Eleventh Five-Year Plan key research project.
At present, the preparation method of domestic and international mosquito-proof textiles mainly contains two kinds: with pesticide emulsion or solution impregnation textiles, handle with adhesive earlier (1) again, and it is fixed on the fabric; (2) be that pesticide is handled with gelatin, Arabic gelatin or amino resins etc., make the microcapsule anophelifuge agent, use adhesive to be fixed on the fabric then.Method (1) shortterm effect effect is better, but not water-fast washing, mosquito-proof persistence is poor; Method (2) has been controlled the evaporation rate of pesticide preferably by microcapsules technology, thereby persistence is better than method (1), but these two kinds of mosquito-proof method for sorting all are to make carrier with adhesive, by physical method anophelifuge are fixed on the fabric, and fastness to washing is poor.Therefore, the mosquito-proof textiles that obtains by these method arrangements all has shortcomings such as poor, the mosquito-proof persistence difference of feel.
Publication number is that the patent of invention of CN 1640260 discloses a kind of mosquito repellent and preparation method, and this mosquito repellent is made up of compound sugar, pyrethroid, water softener and water, makes at 60~80 ℃ of following stirring reaction 12~36h.Publication number is that the patent of invention of CN1641093 then adopts this mosquito repellent to make a kind of mosquito textiles of keeping away, its concrete preparation method is: earlier the mosquito repellent described in the patent of invention of CN 1640260, inorganic neutral sodium-salt, alkaline agent and water are made into dressing liquid by a certain percentage, fabric after will bleaching then places above-mentioned dressing liquid to soak 10~18min, then handle 25~35min, soap at last, wash, drying with alkaline agent.This anti-mosquito cloth has improved the evaporation rate of anophelifuge medicament (pyrethroid) preferably, has slow releasing function preferably, owing to do not use adhesive, thereby its feel, snugness of fit are also better, but in actual the use, its washable intensity is still relatively poor.
[summary of the invention]
Technical problem to be solved by this invention is, overcome the defective of present prior art, a kind of antimosquito finishing agent and preparation method are provided, adopt the anti-mosquito cloth of this finishing agent arrangement, have efficient, lasting, good hand touch, safe characteristics, can be used for making outdoor exercises clothes, military clothes, gardening with clothes, agricultural production with clothes, mosquito net, towelling coverlet, nightwear, window screening etc.
Technical scheme proposed by the invention is:
A kind of antimosquito finishing agent, it comprises following components by part by weight:
Cyclodextrin compounds: 30.0~60.0, culicifuge: 2.0~8.0, surfactant: 0.5~1.5, buffer: 2.7~11.8, catalyst: 8.0~16.0, crosslinking agent 15.0~50.0, can make solid-state antimosquito finishing agent by the said components mixing, add retarder thinner: 20.0~50.0, water: 200~300, just can make liquid antimosquito finishing agent.
In the said components, described buffer can keep the stability of dye bath pH value, reduces aberration, promotes quality, has chelating dispersiveness preferably simultaneously.The combination of buffer preferably phosphoric acid of the present invention, citric acid, carbonic acid, acetic acid, barbiturates and phosphate, hydrophosphate, citrate, carbonate, bicarbonate, acetate, barbiturate, the weight ratio of its combination is elected as: 0.1~2.8: 2.6~9.0.
The combination of one or more in the preferred beta-schardinger dextrin-of described cyclodextrin compounds, DM-, HP-, one chlorotriazine-beta-schardinger dextrin-, hydroxyethyl-, alpha-cyclodextrin and derivative, gamma-cyclodextrin and the derivative thereof.Cyclodextrin compounds exists a hydrophilic outer rim and a hydrophobic cavity in molecular structure, its hydrophobic cavity can form the Subjective and Objective inclusion compound with multiple organic matter.
A kind of in the preferred Metadelphene of described culicifuge, the Permethrin or both combinations.Metadelphene is generally acknowledge in the present world wide a kind of efficient, low toxicity, safe and non-stimulating good broad spectrum activity mosquito-repellent, Permethrin is a pyrethoid insecticides, mosquito had strongly tag, stomach kills and ovicidal action, have and knock down characteristics such as fast, that residual effect is long, be the agent of low poisoning mosquito.
Described surfactant helps improving the inclusion efficient of cyclodextrin to culicifuge, also can improve simultaneously the permeability of fabric, the combination of one or more among the preferred Tween-80 of the present invention, Tween-20, Tween-60, Tween-40, Span-80, Span-60, Span-40, the Span-20;
Described catalyst is preferably magnesium chloride;
Described crosslinking agent is preferably the imidazoles resin of the modification dihydroxymethyl bisethylene urea compound that contains the imidazole ring structure.
Described retarder thinner is preferably a kind of in ethanol, the acetone or both combinations.
The preparation of solid-state antimosquito finishing agent can be adopted following step:
(1) with cyclodextrin compounds, culicifuge, surfactant, buffer, catalyst, crosslinking agent, by weight 30.0~60.0: 2.0~8.0: 0.5~1.5: 2.7~11.8: 8.0~16.0: 15.0~50.0 get the raw materials ready;
(2) buffer being dissolved in parts by weight is in 196.0~250.0 the water, preparation cushioning liquid;
(3) cyclodextrin compounds is dissolved in the described cushioning liquid of step (2), obtains the mixed solution of cyclodextrin and buffering solvent;
(4) add culicifuge, the surfactant of above-mentioned weight portion, add parts by weight again and be 20.0~50.0 retarder thinner and parts by weight and be 4.0~50.0 water, mixing and stirring, preparation mosquito repellent dispersion liquid;
(5) the mosquito repellent dispersant liquid drop is added in the mixed solution of cyclodextrin and buffering solvent,, obtains cyclodextrin/culicifuge inclusion complex in solution at 25.0 ℃~80.0 ℃ following inclusion reaction 2.0~12.0h;
(6) add crosslinking agent, catalyst mix after the cyclodextrin that above-mentioned steps (5) is made/culicifuge inclusion complex in solution drying, just can make solid-state antimosquito finishing agent.
The preparation of liquid antimosquito finishing agent comprises the steps:
(1) with cyclodextrin compounds, culicifuge, surfactant, buffer, catalyst, crosslinking agent, retarder thinner and water by weight 30.0~60.0: 2.0~8.0: 0.5~1.5: 2.7~11.8: 8.0~16.0: 15.0~50.0: 20.0~50.0: 200~300 get the raw materials ready;
(2) buffer being dissolved in parts by weight is in 196.0~250.0 the water, preparation cushioning liquid;
(3) cyclodextrin compounds is dissolved in the described cushioning liquid of step (2), obtains the mixed solution of cyclodextrin and buffering solvent;
(4) add culicifuge, the surfactant of above-mentioned weight portion, add parts by weight again and be 20.0~50.0 retarder thinner and parts by weight and be 4.0~50.0 water, mixing and stirring, preparation mosquito repellent dispersion liquid;
(5) the mosquito repellent dispersant liquid drop is added in the mixed solution of cyclodextrin and buffering solvent,, obtains cyclodextrin/culicifuge inclusion complex in solution at 25.0 ℃~80.0 ℃ following inclusion reaction 2.0~12.0h;
(6) cyclodextrin/culicifuge inclusion complex in solution, crosslinking agent, catalyst are mixed, just can obtain liquid antimosquito finishing agent.
Adopt the anti-mosquito cloth step of above-mentioned antimosquito finishing agent preparation to be:
(1) (also can carry out preliminary treatment earlier in case of necessity, processing method is: cloth boils in 1.5~2.5% alkaline aqueous solution and boils 1.0~1.5h, washes then, and is neutralized to neutrality with 0.3~0.8% acidic aqueous solution, dry getting final product with cloth.) be padded in that (wherein the weight ratio of water and solid-state antimosquito finishing agent is 2~6: 1), the control bath raio is 1.0: 3.0~8.0, and pick-up is 75.0%~100.0% in the mixed liquor of liquid antimosquito finishing agent or solid-state antimosquito finishing agent and water;
(2) preliminary drying 3.0~5.0min under 60.0 ℃~90.0 ℃ temperature conditions bakes 3.0~7.0min again under 130.0 ℃~170.0 ℃ temperature conditions, washing, and drying obtains anti-mosquito cloth
The present invention also can continue the prepared anti-mosquito cloth of step (2) to place 1.0%~20.0% Metadelphene alcohol solution to soak under 25.0 ℃~60.0 ℃, the control bath raio is 1.0: 3.0~5.0, and soak time is 1.0~24.0h.
Wherein, the Metadelphene alcohol solution comprises following components by part by weight:
Metadelphene 1.5~40.0
Surfactant 0.8~1.2
Ethanol 30.0~60.0
Water 100.0
Surfactant in the Metadelphene alcohol solution can be selected one or more the combination among Tween-80, Tween-20, Tween-60, Tween-40, Span-80, Span-60, Span-40, the Span-20 for use.
The present invention by with the culicifuge inclusion in the cavity of cyclodextrin compounds, use the imidazoles resin as crosslinking agent then, add proper additive again and obtain finishing agent, then above-mentioned finishing agent is applied in the fabric processing, and then makes anti-mosquito cloth.Therefore, beneficial effect of the present invention is:
(1) anti-mosquito effect
Mosquito-proof persistent problem is one of very important technical indicator of mosquito-proof textiles, also is that can the mosquito-proof textiles of decision realize one of key technology that industrialization is produced.The mosquito-proof persistence of product of the present invention is mainly reflected in following three aspects: 1. mosquito-proof medicine inclusion has strengthened mosquito-proof stability of drug and slow release greatly in the cyclodextrin compounds inner chamber, and medicine is difficult for running off anti-mosquito effect; 2. by chemical reaction with antimosquito finishing agent securely grafting be fixed on the fabric fibre surface, thereby washability is good, anti-mosquito effect; 3. the grafting internal cavity structure that is fixed on the cyclodextrin compounds on the fabric can also be adsorbed human body because the peculiar smell that sweat etc. produce, and can reduce the information substance of mosquito contact human body like this, reduces the chance of mosquito contact human body, and mosquito-proof effect is strengthened.
(2) safe
Because using, product of the present invention keeps away nontoxic culicifuge Metadelphene (DEET, rat (hero) the acute oral LD of mosquito medicine as WHO (WHO) approval
50=5840mg/kg), Permethrin (rat (hero) the acute oral LD of low toxicity
50>2000mg/kg), be nontoxic/low toxicity material, simultaneously with its inclusion in biodegradable cyclodextrin compounds inner chamber, it is lower that toxicity becomes, and medicine directly do not contact with human body, security is higher, the scope of application is wider.
(3) comfort of fabric is good
Product of the present invention does not use adhesive, and fabric feeling is good, and snugness of fit is good.
(4) processing technology rationally, easily realizes industrialization
The preparation method that the present invention keeps away the mosquito finishing agent is simple, feasible, after improved conventional equipment is kept away mosquito arrangement, can reach desirable keep away mosquito effect, easy realization of industrialization production.
[specific embodiment]
The invention provides a kind of antimosquito finishing agent and preparation method, a kind of anti-mosquito cloth that is made by described antimosquito finishing agent is provided simultaneously, the present invention is described in detail in detail below in conjunction with embodiment.
Embodiment one:
1, the preparation of liquid antimosquito finishing agent:
(1) choose raw material by following weight portion:
B-cyclodextrin 30.0
Permethrin 2.0
Surfactant Tween-80 0.5
Ethanol 20.0
Water 200.0
Citric acid 0.1
Sodium hydrogen phosphate 2.6
Magnesium chloride 8.0
Imidazoles resin 15.0
(2) at normal temperatures and pressures, citric acid and sodium hydrogen phosphate are dissolved in gross weight 98% water preparation cushioning liquid;
(3) beta-schardinger dextrin-is dissolved in cushioning liquid, obtains cyclodextrin cushioning liquid;
(4) with the water of Permethrin, Tween-80, ethanol, gross weight 2%, mixing and stirring prepares the mosquito repellent dispersion liquid;
(5) the mosquito repellent dispersant liquid drop is added in the cyclodextrin cushioning liquid,, obtains cyclodextrin/culicifuge inclusion complex in solution at 25.0 ℃ of following inclusion reaction 12.0h;
(6) cyclodextrin/culicifuge inclusion complex in solution, imidazoles resin, magnesium chloride are mixed, can obtain liquid antimosquito finishing agent.
2, the preparation of anti-mosquito cloth:
1) cloth is boiled in 1.5% sodium hydrate aqueous solution boil 1.0h, washing then, and be neutralized to neutrality, drying for standby with 0.3% aqueous citric acid solution;
2) under the room temperature, the cloth after will handling through step 1) is padded in the liquid antimosquito finishing agent, control bath raio 1.0: 3.0, and two soak two rolls, and making its pick-up is 75.0%;
3) preliminary drying 5.0min under 60.0 ℃ of temperature bakes 7.0min under 130.0 ℃ of conditions, and the washing back is dry, can make anti-mosquito cloth.
Embodiment two:
1, the preparation of solid-state antimosquito finishing agent:
(1) choose raw material by following weight portion:
Dimethyl-30.0
Beta-schardinger dextrin-, 20.0
Permethrin 3.0
Surfactant Tween-80 0.5
Surfactant Tween-60 0.5
Acetone 30.0
Water 250.0
Phosphatase 11 .0
Dibastic sodium phosphate 3.6
Magnesium chloride 10.0
Imidazoles resin 20.0
(2) at normal temperatures and pressures, it is in 94% water that phosphoric acid and dibastic sodium phosphate are dissolved in gross weight, preparation cushioning liquid;
(3) beta-schardinger dextrin-, dimethyl-are dissolved in the cushioning liquid, obtain cyclodextrin cushioning liquid;
(4) with Permethrin, Tween-80, Tween-60, acetone, gross weight be 4% water, mixing and stirring, preparation mosquito repellent dispersion liquid;
(5) the mosquito repellent dispersant liquid drop is added in the cyclodextrin cushioning liquid,, obtains cyclodextrin/culicifuge inclusion complex in solution at 40.0 ℃ of following inclusion reaction 8.0h;
(6) cyclodextrin/culicifuge inclusion complex in solution is dried to water content and is lower than 1% back adding imidazoles resin, magnesium chloride, can obtain solid-state antimosquito finishing agent.
2, the preparation of anti-mosquito cloth:
1) cloth is boiled in 1.8% sodium hydrate aqueous solution boil 1.0h, washing then, and be neutralized to neutrality, drying for standby with 0.55% aqueous citric acid solution;
2) earlier solid-state antimosquito finishing agent and water are mixed with liquid antimosquito finishing agent by 1: 5 weight ratio, then at room temperature, the cloth after will handling through step 1) is padded in the liquid antimosquito finishing agent, controls bath raio 1.0: 5.0, two soak two rolls, and making its pick-up is 90.0%;
3) preliminary drying 4.0min under 70.0 ℃ of temperature bakes 5.0min under 150.0 ℃ of conditions, and the washing back is dry, can make anti-mosquito cloth.
Embodiment three:
1, the preparation of liquid antimosquito finishing agent:
(1) choose raw material by following weight portion:
Hydroxyethyl-55.0
Metadelphene 2.0
Permethrin 3.0
Surfactant Tween-80 0.25
Surfactant Tween-60 0.25
Surfactant Span-60 0.5
Ethanol 25.0
Acetone 20.0
Water 250.0
Acetic acid 2.0
Sodium acetate 6.5
Magnesium chloride 12.0
Imidazoles resin 30.0
(2) at normal temperatures and pressures, in acetic acid and sodium acetate water-soluble (gross weight 92%), preparation cushioning liquid;
(3) hydroxyethyl-is dissolved in cushioning liquid, obtains cyclodextrin cushioning liquid;
(4) with Permethrin, Metadelphene, surfactant Tween-80, Tween-60, Span-60, ethanol, acetone, water (gross weight 8%) mixing and stirring, preparation mosquito repellent dispersion liquid;
(5) the mosquito repellent dispersant liquid drop is added in the cyclodextrin cushioning liquid,, obtains cyclodextrin/culicifuge inclusion complex in solution at 60.0 ℃ of following inclusion reaction 10.0h;
(6) cyclodextrin/culicifuge inclusion complex in solution, imidazoles resin, magnesium chloride are mixed, can obtain liquid antimosquito finishing agent.
2, the preparation of Metadelphene alcohol solution:
Choose raw material by following weight portion:
Metadelphene 10.0
Surfactant Tween-80 0.8
Ethanol 30.0
Water 100.0
Mix and get final product.
3, the preparation of anti-mosquito cloth:
1) under the room temperature, cloth is padded in the liquid antimosquito finishing agent, control bath raio 1.0: 4.0, two soak two rolls, and making its pick-up is 85.0%;
2) preliminary drying 4.0min under 80.0 ℃ of temperature bakes 6.0min under 160.0 ℃ of conditions;
3) fabric is continued to be soaked in the Metadelphene alcohol solution for preparing under 25.0 ℃, control bath raio 1.0: 3.0, soak time is 5.0h, the washing back is dry; Can make anti-mosquito cloth.
Embodiment four:
1, the preparation of liquid antimosquito finishing agent:
(1) choose raw material by following weight portion:
One chlorotriazine beta-schardinger dextrin-25.0
Alpha-cyclodextrin 20.0
HP-10.0
DM-5.0
Metadelphene 3.0
Permethrin 5.0
Surfactant Tween-80 1.0
Surfactant Span-20 0.5
Ethanol 25.0
Acetone 25.0
Water 300.0
Citric acid 0.1
Sodium hydrogen phosphate 9.0
Magnesium chloride 12.0
Imidazoles resin 50.0
(2) at normal temperatures and pressures, in citric acid and sodium hydrogen phosphate water-soluble (gross weight 90%), preparation cushioning liquid;
(3) a chlorotriazine beta-schardinger dextrin-, alpha-cyclodextrin, HP-, DM-are dissolved in cushioning liquid, obtain cyclodextrin cushioning liquid;
(4) with Permethrin, Metadelphene, surfactant Tween-80, Span-20, ethanol, acetone, water (gross weight 10%) mixing and stirring, preparation mosquito repellent dispersion liquid;
(5) the mosquito repellent dispersant liquid drop is added in the cyclodextrin cushioning liquid,, obtains cyclodextrin/culicifuge inclusion complex in solution at 80.0 ℃ of following inclusion reaction 2.0h;
(6) cyclodextrin/culicifuge inclusion complex in solution, imidazoles resin, magnesium chloride are mixed, can obtain liquid antimosquito finishing agent.
2, the preparation of Metadelphene alcohol solution:
Choose raw material by following weight portion:
Metadelphene 40.0
Surfactant Tween-80 0.8
Surfactant Span-20 0.4
Ethanol 60.0
Water 100.0
Mix and get final product.
3, the preparation of anti-mosquito cloth:
1) cloth is boiled in 2.5% sodium hydrate aqueous solution boil 1.2h, washing then, and be neutralized to neutrality, drying with 0.8% the acetic acid aqueous solution;
2) under the room temperature, cloth is padded in the liquid antimosquito finishing agent, control bath raio 1.0: 8.0, two soak two rolls, and making its pick-up is 100.0%;
3) preliminary drying 5.0min under 90.0 ℃ of temperature bakes 3.0min under 170.0 ℃ of conditions;
4) fabric is continued to be soaked under 60.0 ℃ prepare the Metadelphene alcohol solution in, control bath raio 1.0: 5.0, soak time is 24.0h, the washing back is dry; Can make anti-mosquito cloth.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.