CN102771501A - Composite mildewproof and antibacterial agent and its preparation method - Google Patents

Composite mildewproof and antibacterial agent and its preparation method Download PDF

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Publication number
CN102771501A
CN102771501A CN2011101243825A CN201110124382A CN102771501A CN 102771501 A CN102771501 A CN 102771501A CN 2011101243825 A CN2011101243825 A CN 2011101243825A CN 201110124382 A CN201110124382 A CN 201110124382A CN 102771501 A CN102771501 A CN 102771501A
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China
Prior art keywords
antibacterial agent
composite mildewproof
fumarate
composite
camphor
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CN2011101243825A
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Chinese (zh)
Inventor
车宏伟
刘晓静
钱亮
刘星海
鄢国平
王晓燕
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Shenzhen Guobao Coinage Co Ltd
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Shenzhen Guobao Coinage Co Ltd
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Priority to CN2011101243825A priority Critical patent/CN102771501A/en
Publication of CN102771501A publication Critical patent/CN102771501A/en
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Abstract

The invention discloses a composite mildewproof and antibacterial agent and its preparation method. The antibacterial agent comprises an active component and a slow release carrier accounting for 20-60% of the total mass of the composite mildewproof and antibacterial agent. The active component is prepared from the following raw materials by weight part: 3-25 of fumarate, 0.5-10 of rich-d-t-empenthrin, and 70-95 of camphor. The preparation method consists of: putting the raw materials into dichloromethane, conducting mixing to make all raw materials completely dissolved, then volatilizing the solvent, preparing the remaining solid into powder, tablets, blocks or granules, and carrying out split packaging to obtain small solid packs of the product. The composite mildewproof and antibacterial agent disclosed in the invention has the advantages of broad mildewproof and antibacterial spectrum, wide application range, applicability to different environments, and slow release of the active component, as well as simple and reliable preparation method.

Description

A kind of composite mildewproof antibacterial agent and preparation method thereof
Technical field
The present invention relates to a kind of antimildew and antibacterial agent and preparation method thereof, relate in particular to a kind of composite mildewproof antibacterial agent and preparation method thereof.
Background technology
Along with the development of society and the raising of living standards of the people, people to the quality of living environment and health level require increasingly high.Various pathogenic microorganismss (like bacterium, fungi, virus etc.) are distributing in natural environment; Under certain condition pathogenic microorganisms can ramp, breeding; Even morph; Not only can cause the decomposition, rotten and corrupt of various materials, grain, feed etc., and threaten human beings'health.Therefore, in order to promote health, making the life better and working environment, research and develop the good antimildew and antibacterial agent of novel, efficient, nonpoisonous and tasteless and antibiotic enduring quality, is one of emphasis direction of antimildew and antibacterial investigation of materials and development.
Antibacterial agent can reduce three types of organic antibacterial agent, inorganic antiseptic, natural antibacterial agents etc.These antibacterial agents generally have only single sterilization component, and sterilization object is comparatively single, are difficult to accomplish to kill the purpose of multiple pathogenic microorganisms.Though the heat resisting temperature of inorganic antiseptic is higher, service life is longer, receive the restriction of occasion and condition when using; Advantages such as sterilization speed is fast though organic antibacterial agent has, anti-microbial property is good, micromolecular organic antibacterial agent have poor heat resistance, easy decomposition, service life than shortcomings such as weak points.The extraction of natural antibacterial agent is difficulty, and less stable also exists poor heat resistance, easy decomposition, service life than shortcomings such as weak points.
Summary of the invention
The technical problem that the present invention will solve is; Single to antimildew and antibacterial agent effect in the prior art, can't kill restriction, organic antibacterial agent poor heat resistance that multiple harmful germ, inorganic antiseptic receive use occasion and service condition simultaneously, be prone to decompose, defective that service life is short, provide a kind of have wide spectrum antimildew and antibacterial, range of application wide, be suitable for the varying environment and the slow composite mildewproof antibacterial agent of release of active ingredients.
The technical problem that the present invention further will solve is, a kind of preparation method of composite mildewproof antibacterial agent of simple and reliable process is provided.
The technical solution adopted for the present invention to solve the technical problems is: a kind of composite mildewproof antibacterial agent, comprise active component and slow-released carrier, and wherein said slow-released carrier accounts for the 20-60% of composite mildewproof antibacterial agent gross mass; Said active component is processed by the raw material of following parts by weight:
Fumarate 3-25
The trans Prallethrin 0.5-10 of rich dextrorotation
Camphor 70-95.
Said active component is preferably processed by the raw material of following parts by weight:
Fumarate 10
The trans Prallethrin 2.5 of rich dextrorotation
Camphor 87.5.
In the composite mildewproof antibacterial agent, described fumarate is preferably a kind of in dimethyl fumarate, DEF, fumaric acid dipropyl, dibutyl fumarate, monomethyl fumarate, monomethyl ester, fumaric acid list propyl ester, the fumaric acid mono.
In the composite mildewproof antibacterial agent, said fumarate is dimethyl fumarate or monomethyl fumarate most preferably.
In the composite mildewproof antibacterial agent, said camphor is preferably natural camphor or synthetic camphor.
In the composite mildewproof antibacterial agent, said slow-released carrier is preferably the degradable high polymer material carrier.
In the composite mildewproof antibacterial agent, the homopolymers of the monomer that said degradable high polymer material carrier is lactic acid, carbonic ester, phosphate, ortho esters, acid anhydrides and at least two kinds copolymer in them thereof.
In the composite mildewproof antibacterial agent, said slow-released carrier is a polyvinyl acetate.
A kind of preparation method of composite mildewproof antibacterial agent drops into raw material in the carrene, stirs to make all raw materials dissolve fully, then solvent evaporates is fallen, and the residue solids is processed powdery, sheet, bulk or graininess, and the solid inner wrapping of product is processed in packing; Said raw material comprises active component and slow-released carrier, and wherein said slow-released carrier accounts for the 20-60% of composite mildewproof antibacterial agent gross mass; Said active component is processed by the raw material of following parts by weight: fumarate 3-25, the trans Prallethrin 0.5-10 of rich dextrorotation and camphor 70-95.
Among the preparation method of composite mildewproof antibacterial agent, said solvent evaporates is meant at room temperature, and the carrene that dissolves raw material is vapored away naturally, perhaps carrene is evaporated under normal pressure or decompression.
Composite mildewproof antibacterial agent of the present invention is divided into active component and slow-released carrier two parts; Wherein active component is with three kinds of different antimildew and antibacterial agents: fumarate, camphor and empenthrin are compound in proportion; Each tool chief of these three kinds of active components, wherein the bacteriostatic activity body of fumarate is the molecular state of fumarate, is in the fumarate of molecular state; Can penetrate the cells of microorganisms film smoothly; Be penetrated in the cell, suppress the division and the breathing of microbial cell, thus the growth and breeding of effective controlling microbial.Many moulds there is special inhibition effect, and has antimycotic ability.The antibacterial activity of fumarate does not receive the influence of pH value, and has insecticidal activity concurrently, also has and tags or fumigation action.Rich empenthrin has very high vapour pressure at normal temperatures, insect is had fast knock down, smoked kill or repellent action, and multiple Dermestidae beetle had outstanding prevention feeding effect.Be mainly used in house pests such as control housefly, mosquito, lice, cockroach.Camphor is prone to distillation, by the solid-state gas that directly changes into, produces irritating smell; In among a small circle, be full of the camphor molecule, insects absorb the camphor molecule of trace behind temporary sedation, promptly cause corticocerebral excitement; Cause insane appearance spasm, last owing to absorb depleted and even dead.Camphor has remarkable antifungic action, can resist gold-coloured staphylococci, wool appearance sporidiole bacteria, Trichophyton rubrum etc., and camphor has good external anti-demodectic effect in addition, and mechanism is direct action of contace poison and neuromuscular toxic action.
Best antimildew and antibacterial effect be can reach after three kinds of active components of composite mildewproof antibacterial agent of the present invention cooperate, the scope of application, the effect of enhancing antimildew and antibacterial of antimildew and antibacterial agent enlarged.The present invention mixes several kinds of active components according to a certain percentage; Not only widen greatly antimicrobial spectrum, can complementary synergy, improve the antimildew and antibacterial performance, reduce aspects such as side effect and all have obvious advantage; But also can reduce the consumption of single antimildew and antibacterial composition; To reach best antimildew and antibacterial effect, the present invention has enlarged the scope of application of antimildew and antibacterial agent, the action effect of enhancing antimildew and antibacterial.
The present invention utilizes slow-released carrier, can effectively control the rate of release of active component, makes antimildew and antibacterial agent by design dosage, in the time range that requires, slowly discharges by certain speed, to reach the purpose that prolongs antimildew and antibacterial, improves the availability of antimildew and antibacterial agent.Experimental result shows that the composite mildewproof antibacterial agent of the present invention's preparation has slowly-releasing, controlled-release function, slows down the rate of release of antimildew and antibacterial agent, and makes its stable discharging, and has improved availability, safety and the validity of antimildew and antibacterial agent; Slowly-releasing composite mildewproof antibacterial agent all has very strong inhibitory action to growth and the breeding of Escherichia coli, mould, aspergillus, Mucor.
Slow-released carrier of the present invention has been selected degradable polymeric carrier material; Can in environment, progressively degrade at carrier material after the use; Resolve into the micromolecular compound of environmentally safe, can or divide and take off, do not have material residual by the environment absorption; There is not the post processing problem, can not pollute surrounding environment.
The present invention adopts the method for organic solvent with the dissolving of all raw materials, and simple and reliable process makes raw material mixing as far as possible, and antimildew and antibacterial agent is evenly distributed in polymer carrier, makes that the rate of release of antimildew and antibacterial agent is stable.
Description of drawings
To combine accompanying drawing and embodiment that the present invention is described further below, in the accompanying drawing:
Fig. 1 is the weight loss rate of synthetic camphor powder and dimethyl fumarate;
Fig. 2 is the rate of release of composite mildewproof antibacterial agent of the present invention under 55 ℃;
Fig. 3 is a composite mildewproof antibacterial agent of the present invention rate of release at room temperature;
Fig. 4 is the OD value change curve of the inoculum of different time under the composite mildewproof antibacterial agent of the present invention effect;
Fig. 5 is that inoculum OD value is with the change curve that adds the different antibiotic dosage of composite mildewproof of the present invention of concentration;
Fig. 6 is the bacterium size that falls after the Mucor behind the antibiotic dosage of adding composite mildewproof of the present invention grew up 7 days;
Fig. 7 is the bacterium size that falls that does not add after Mucor behind the antibiotic dosage of composite mildewproof of the present invention grew up 7 days.
Embodiment
A kind of composite mildewproof antibacterial agent comprises active component and slow-released carrier, and wherein said slow-released carrier accounts for the 20-60% of composite mildewproof antibacterial agent gross mass; Said active component is processed by the raw material of following parts by weight:
Fumarate 3-25
The trans Prallethrin 0.5-10 of rich dextrorotation
Camphor 70-95.
Said active component is preferably processed by the raw material of following parts by weight:
Fumarate 10
The trans Prallethrin 2.5 of rich dextrorotation
Camphor 87.5.
In the composite mildewproof antibacterial agent, described fumarate is preferably a kind of in dimethyl fumarate, DEF, fumaric acid dipropyl, dibutyl fumarate, monomethyl fumarate, monomethyl ester, fumaric acid list propyl ester, the fumaric acid mono.
In the composite mildewproof antibacterial agent, said fumarate is dimethyl fumarate or monomethyl fumarate most preferably.
Among following examples 1-7, fumarate is selected dimethyl fumarate, monomethyl fumarate, DEF, fumaric acid dipropyl, dibutyl fumarate, monomethyl ester, fumaric acid list propyl ester and fumaric acid mono respectively.
In the composite mildewproof antibacterial agent, said camphor is preferably natural camphor or synthetic camphor.Among following examples 1-7, preceding four embodiment select natural camphor, and back three embodiment select synthetic camphor.
In the composite mildewproof antibacterial agent, said slow-released carrier is preferably the degradable high polymer material carrier.
In the composite mildewproof antibacterial agent, the homopolymers of the monomer that said degradable high polymer material carrier is lactic acid, carbonic ester, phosphate, ortho esters, acid anhydrides and at least two kinds copolymer in them thereof.The homopolymers of the monomer of lactic acid, carbonic ester, phosphate, ortho esters, acid anhydrides is respectively PLA, Merlon, polyphosphate, poe, gathers acid anhydrides.
Said slow-released carrier can also be polyvinyl acetate.
Among following examples 1-7; Slow-released carrier is selected the copolymer of PLA, Merlon, polyphosphate, poe, the copolymer that gathers acid anhydrides, polyvinyl acetate, lactic acid and carbonic ester, phosphate and ortho esters respectively; Except above-mentioned selection; Can also be the copolymer of lactic acid, carbonic ester and phosphate, or the copolymer of phosphate, ortho esters, acid anhydrides substitute the slow-released carrier of the foregoing description.
The preparation method of composite mildewproof antibacterial agent is: all raw materials are dropped in the carrene, and stirring makes all raw materials dissolve fully, and the carrene that at room temperature will dissolve raw material volatilizees naturally, perhaps carrene is evaporated under normal pressure or decompression.The residue solids is processed powdery, sheet, bulk or graininess, processes the product of solid inner wrapping after the packing.Embodiment of the invention 1-7 processes sheet, bulk or graininess respectively.
Following table is among the embodiment 1-7, the raw material weight umber:
Figure BDA0000061166320000071
1, the mensuration of composite mildewproof antibacterial agent weight loss rate in slow-released carrier
Fig. 1 is single synthetic camphor powder and dimethyl fumarate, under 55 ℃ constant temperature, measures its aerial weight loss rate.Experimental result shows that when no slow-released carrier, the weight loss rate of antimildew and antibacterial agent almost is linear with the time, does not have slowly-releasing, controlled release phenomenon, and the weight-loss ratio of synthetic camphor powder and dimethyl fumarate reaches 91.6% and 52.86% respectively when 17h.This shows that the aerial rate of release of antimildew and antibacterial agent is too fast, and drug effect is too short when causing using, if will prolong its service time, then need strengthen its dosage.
Fig. 2 is that slow-released carrier content is the weight loss rate of composite mildewproof antibacterial agent of the present invention under 55 ℃ constant temperature of 20-50%.Compared to Figure 1, after antimildew and antibacterial agent was carrier with the macromolecular material, its weight loss rate obviously reduced, and rate of release reduces along with the increase of slow-released carrier content.Therefore the high molecular slow-release carrier has slowly-releasing, controlled release effect to antimildew and antibacterial agent, makes the compound antimildew and antibacterial agent of slowly-releasing have more stable antimildew and antibacterial effect, prolongs its service life.Through regulating the content of slow-released carrier, and the ratio of antimildew and antibacterial agent, can control the rate of release of compound antimildew and antibacterial agent.
Fig. 3 can find out; The rate of release of composite mildewproof antibacterial agent of the present invention reduces along with the increase of slow-released carrier content gradually; Under room temperature environment, after 19 months release, the content of slow-released carrier is the weight loss rate of 30% composite mildewproof antibacterial agent; Be higher than vector contg and be the weight loss rate of 40%, 50% composite mildewproof antibacterial agent, its weight loss rate is respectively 40.82%, 30.95%, 23.87%.Experimental result shows; Composite mildewproof antibacterial agent of the present invention has good slowly-releasing, controlled-release function; Antimildew and antibacterial agent was discharged with more stable speed in a very long time, and Use Limitation, minimizing using dosage and reduction side effect to prolonging antimildew and antibacterial agent play very big effect.
2, germ experiment
The bacterial classification of this experimental selection be in the bacterium the most extensively, and representative Escherichia coli reference culture (Ecoli TGl), medium is the LB medium.This experiment adds the composite mildewproof antibacterial agent of the present invention of different content through in the medium that contains bacterium, measures the OD value situation of change of culture fluid under different time, the condition, thereby detects the antimildew and antibacterial effect of composite mildewproof antibacterial agent of the present invention.
Fig. 4 is the time dependent curve of culture fluid OD value, and 0 expression does not add composite mildewproof antibacterial agent of the present invention (being control curve), and 10g/L, 20g/L, 40g/L are the curve that adds composite mildewproof antibacterial agent of the present invention in the medium.Experimental result shows; After adding slowly-releasing composite bactericidal material; Culture fluid OD value during OD value comparison in the culture fluid is according to the facts tested is little, and bacteriostasis is that obviously enhancing is not grown when 40g/L basically along with the increase of the antibiotic dosage of adding composite mildewproof of the present invention.From Fig. 4, can draw, composite mildewproof antibacterial agent of the present invention has played certain inhibitory action to the growth of bacterium.
Fig. 5 is the change curve of inoculum OD value with the different antibiotic dosage of composite mildewproof of the present invention of adding concentration.Experimental result shows that the OD value of inoculum is along with the increase that adds composite mildewproof antibacterial agent concentration of the present invention, and the OD value of inoculum reduces gradually.When the composite mildewproof antibacterial agent concentration of the present invention that adds is the 40g/L left and right sides; If increase the composite mildewproof antibacterial agent concentration of the present invention that adds again; The OD value of bacterium liquid changes little; Therefore, when using according to 40g/L dosage, composite mildewproof antibacterial agent of the present invention is the growth and the breeding of ability good restraining, kill bacteria just.
3, fungi experiment
Choose mould, aspergillus, three kinds of fungies of Mucor and experimentize, put three kinds of different fungies respectively in plate central authorities.The composite mildewproof antibacterial agent that around bacterium colony, adds doses is contrast with the plate that does not add composite mildewproof antibacterial agent of the present invention simultaneously, puts into 28 ℃ of incubators and cultivates a week, observes the variation of bacterium colony size.
Experimental result shows that after being added with composite mildewproof antibacterial agent of the present invention, the drop point of all fungies is littler than fungi drop point in the corresponding blank.Composite mildewproof antibacterial agent of the present invention all has certain antimildew and antibacterial ability to mould, aspergillus, three kinds of fungies of Mucor, can play the effect of antimildew and antibacterial.Like Fig. 6, the 7th, the contrast picture of trichobacteria growth; Be added with composite mildewproof antibacterial agent of the present invention among Fig. 6; Fig. 7 is the blank that does not add composite mildewproof antibacterial agent of the present invention; The result show be added with composite mildewproof antibacterial agent of the present invention after, the diameter of its fungi drop point has only 1/3 of fungi drop point diameter in the blank.Same composite mildewproof antibacterial agent of the present invention has also drawn same conclusions to the related experiment of black mould, mould, and therefore, composite mildewproof antibacterial agent of the present invention all has certain inhibitory action to three kinds of fungi growth.

Claims (10)

1. a composite mildewproof antibacterial agent is characterized in that, comprises active component and slow-released carrier, and wherein said slow-released carrier accounts for the 20-60% of composite mildewproof antibacterial agent gross mass; Said active component is processed by the raw material of following parts by weight:
Fumarate 3-25
The trans Prallethrin 0.5-10 of rich dextrorotation
Camphor 70-95.
2. composite mildewproof antibacterial agent according to claim 1 is characterized in that, said active component is processed by the raw material of following parts by weight:
Fumarate 10
The trans Prallethrin 2.5 of rich dextrorotation
Camphor 87.5.
3. composite mildewproof antibacterial agent according to claim 1 and 2; It is characterized in that described fumarate is a kind of in dimethyl fumarate, DEF, fumaric acid dipropyl, dibutyl fumarate, monomethyl fumarate, monomethyl ester, fumaric acid list propyl ester, the fumaric acid mono.
4. composite mildewproof antibacterial agent according to claim 3 is characterized in that, said fumarate is selected dimethyl fumarate or monomethyl fumarate.
5. composite mildewproof antibacterial agent according to claim 1 and 2 is characterized in that, said camphor is natural camphor or synthetic camphor.
6. composite mildewproof antibacterial agent according to claim 1 and 2 is characterized in that, said slow-released carrier is the degradable high polymer material carrier.
7. composite mildewproof antibacterial agent according to claim 6 is characterized in that, the homopolymers of the monomer that said degradable high polymer material carrier is lactic acid, carbonic ester, phosphate, ortho esters, acid anhydrides and at least two kinds copolymer in them thereof.
8. composite mildewproof antibacterial agent according to claim 1 and 2 is characterized in that, said slow-released carrier is a polyvinyl acetate.
9. the preparation method of a composite mildewproof antibacterial agent is characterized in that, raw material is dropped in the carrene; Stirring makes all raw materials dissolve fully; Then solvent evaporates is fallen, the residue solids is processed powdery, sheet, bulk or graininess, and the solid inner wrapping of product is processed in packing; Said raw material comprises active component and slow-released carrier, and wherein said slow-released carrier accounts for the 20-60% of composite mildewproof antibacterial agent gross mass; Said active component is processed by the raw material of following parts by weight: fumarate 3-25, the trans Prallethrin 0.5-10 of rich dextrorotation and camphor 70-95.
10. the preparation method of composite mildewproof antibacterial agent according to claim 9 is characterized in that, said solvent evaporates is meant at room temperature, and the carrene that dissolves raw material is vapored away naturally, perhaps carrene is evaporated under normal pressure or decompression.
CN2011101243825A 2011-05-13 2011-05-13 Composite mildewproof and antibacterial agent and its preparation method Pending CN102771501A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106519821A (en) * 2016-10-28 2017-03-22 中山市丽莎涂料有限公司 Anti-mildew agent, anti-mildew coating and preparing method of anti-mildew coating
CN117656630A (en) * 2024-02-01 2024-03-08 广东骊虹新材料有限公司 High-strength multilayer composite packaging film material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100998332A (en) * 2007-01-18 2007-07-18 陈连 Environmental protection type moth-proof and mould-proof dust
CN101798465A (en) * 2010-03-16 2010-08-11 龙海市奈特化工有限责任公司 Composite material capable of releasing volatile substances persistently and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100998332A (en) * 2007-01-18 2007-07-18 陈连 Environmental protection type moth-proof and mould-proof dust
CN101798465A (en) * 2010-03-16 2010-08-11 龙海市奈特化工有限责任公司 Composite material capable of releasing volatile substances persistently and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106519821A (en) * 2016-10-28 2017-03-22 中山市丽莎涂料有限公司 Anti-mildew agent, anti-mildew coating and preparing method of anti-mildew coating
CN106519821B (en) * 2016-10-28 2018-12-21 中山市丽莎涂料有限公司 A kind of mould resistant and a kind of anti-mildew paint and preparation method thereof
CN117656630A (en) * 2024-02-01 2024-03-08 广东骊虹新材料有限公司 High-strength multilayer composite packaging film material and preparation method thereof
CN117656630B (en) * 2024-02-01 2024-04-16 广东骊虹新材料有限公司 High-strength multilayer composite packaging film material and preparation method thereof

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Application publication date: 20121114