CN101473847A - Composite anti-bacteria agent as well as preparation method and use thereof - Google Patents
Composite anti-bacteria agent as well as preparation method and use thereof Download PDFInfo
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- CN101473847A CN101473847A CN 200910036823 CN200910036823A CN101473847A CN 101473847 A CN101473847 A CN 101473847A CN 200910036823 CN200910036823 CN 200910036823 CN 200910036823 A CN200910036823 A CN 200910036823A CN 101473847 A CN101473847 A CN 101473847A
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- chitin
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- complex antimicrobials
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Abstract
The invention discloses a compound antibacterial agent formed by complexing chitin derivative, medical stone and metal ions, wherein, the metal ions comprise Ca<2+>, Zn<2+>, Cu<2+>, Ba<2+> and Al<3+>. The invention also provides a preparation method for the compound antibacterial agent, and the method comprises the following steps: the chitin derivative aqueous solution with the weight percentage of 1 percent to 10 percent is prepared, then the medical stone with the mass ratio of 1:1 to 1.5 is added for mixing according to the chitin derivative aqueous solution, then the saturated metal ion solution with the weight percentage of 20 percent is added for filtering after complexing, and then the filter residues are dried. The invention also provides an application of the compound antibacterial agent in the preparation of the fresh-keeping antibiotic plastics, i.e., the compound antibacterial agent is used for preparing the master batch. The invention has the advantages that the price of the raw material of the compound antibacterial agent is low, the method for preparing the master batch is simple, the produced preservative film has good fresh-keeping effect, bacteria resistant effect and good mold-proof effect, and the invention is easy for the popularization and the application of the industrial production.
Description
Technical field
The present invention relates to a kind of complex antimicrobials and its production and application, especially a kind of complex antimicrobials of preparing in the anti-bacterial refreshing plastics and its production and application that is used to.
Background technology
China is world-class vegetables and fruits big producing country and sells big country, yet vegetables and fruits have the vegetables and fruits loss about 30% in storage, transportation and sales process, and every year, only this loss was just up to 75,000,000,000 yuan, and the economic benefit that has had a strong impact on China increases.Trace it to its cause packaging material improper use or lacking packing is to cause the rot major reason of loss of vegetables and fruits.Common plastic film is used for packing, and oxygen permeability is relatively poor, when carrying out the packing of fresh food such as vegetables and fruits with it, causes CO in the packing container easily
2Excessive concentration O
2Concentration low excessively, make food carry out anaerobic respiration, be absorbed in disorder and putrid and deteriorated, because respiration and transpiration produce moisture, form moist environment simultaneously, caused growing, breed of bacterium, quickened the rotten rotten of vegetables and fruits.
At present, domestic relevant antimicrobial preservative film development is generally adopted and is added carrying silver antimicrobials in plastics preparation anti-bacterial refreshing master batch, the packing that is used for food, but because carrying silver antimicrobials is on the high side, and add easy oxidation stain in man-hour, so this method large-scale industrialization production has been subjected to bigger restriction.Prior art is used the antibacterial agent that the derivative by the natural polymer chitin makes in addition: water miscible carboxymethyl chitin, shitosan itself have good antibacterial and mouldproof effect, yet the processing temperature that surpasses 100 ℃ can make it decompose carbonization, its dry product of while also can't become fine powder and join in the plastics, because it at high temperature decomposes carbonization easily, be subjected to the influence of processing conditions, can only adopt the method for filming to add at present, industrial production is subjected to bigger limitation, also fails to be applied in the large-scale industrial production.
Summary of the invention
Technical problem to be solved by this invention is the difficulty that overcomes prior art, and it is a kind of effectively antibiotic and prevent the complex antimicrobials that vegetables and fruits are rotten, that cost is low, resistant to elevated temperatures, can make full use of chitin derivativ that purpose is to provide.
Another object of the present invention provides the preparation method of the above-mentioned complex antimicrobials of a kind of advantages of simplicity and high efficiency.
A further object of the invention provides the application of above-mentioned complex antimicrobials.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of complex antimicrobials is formed by chitin derivativ, medical stone and complexing of metal ion, and described metal ion is Ca
2+, Zn
2+, Cu
2+, Ba
2+, Al
3+
Described chitin derivativ is selected from carboxymethyl chitin, carboxyethyl chitin, carboxymethyl ethyl chitin, carboxylic propyl group chitin, carboxylic butyl chitin, CMC, carboxyetbyl chitosan, carboxymethyl ethyl chitosan or carboxylic butyl shitosan.
Complex antimicrobials of the present invention adopts water miscible chitin derivativ, itself has good antibacterial and mouldproof effect, yet the processing temperature above 100 ℃ can make it decompose carbonization, and its dry product of while also can't become fine powder and join in the plastics.For overcoming this shortcoming, the present invention has introduced medical stone in the middle of component, medical stone itself also has stronger bacteriostasis efficacy, and the processing temperature that can improve medical stone with the method for complexation of metal ions to be adapting to the processing of plastic temperature, and can become fine powder and join in the plastics.The present invention utilizes the carrier of medical stone as antibacterial agent, in water slurry, add metal ion, make free metal ion and the metal ion in the medical stone and water-solubility chitin derivative form controlled part complex compound and attached on the medical stone, drying is pulverized and is made complex antimicrobials, overcome carboxymethyl chitin, CMC is limited by processing temperature, be difficult to join the shortcoming in the plastics, kept the characteristics of both original antibacterial and mouldproofs simultaneously.
The preparation method of above-mentioned complex antimicrobials is:
The preparation weight percent concentration is 1%～10% the chitin derivativ aqueous solution, press the chitin derivativ aqueous solution again: the medical stone quality is than adding medical stone for 1:1～1.5, mixing, add an amount of weight ratio concentration then and be 15～30% saturated metal ion solution, filter after the complexing, filter residue and drying promptly.
Free metal ion generation complex reaction in the metal ion of complex antimicrobials employing chitin derivativ of the present invention and interpolation and the medical stone, the high efficiency of additive capability that keeps medical stone simultaneously, through the double action of chemistry, obtain being used to prepare the pressed powder with antibacterial and mouldproof of vinyon at last with physics.
The present invention also provides the application of above-mentioned complex antimicrobials in the fresh-keeping antibiotic plastic of preparation.
Described application in the fresh-keeping antibiotic plastic of preparation is that described complex antimicrobials is used to prepare master batch.
Describedly complex antimicrobials is used to prepare master batch such as preferred version is: with 20～50 weight portion complex antimicrobials, 50～80 weight portion low density polyethylene (LDPE) (LDPE) 1F7B, 5～10 weight portion SiO
2, 2～5 weight portion KMnO
4, 0.1～0.5 weight portion Arlacel-20,1～2 weight portion fusing point is 50～80 ℃ a paraffin, makes the material of kneading; The material of kneading makes master batch through extruding pelletization; Extrusion temperature is: 130 ℃～170 ℃.
The above-mentioned master batch that makes can further be made various plastics as required.
Compared with prior art, except above-mentioned beneficial effect, the present invention also has following beneficial effect:
Complex antimicrobials raw material chitin derivativ of the present invention is natural prodcuts, cost is low, the price of other raw materials is also cheaper, the complex antimicrobials preparation method is simple, and the antibacterial agent that makes can be high temperature resistant, improves processing temperature in preparation process, make it can under the process conditions of plastic shaping, still keep good antibacterial effect, with the plastic blend moulding, also be outstanding feature of the present invention, have not yet to see the relevant report that relates to this aspect.
Complex antimicrobials of the present invention is applied to prepare plastic package material, has fresh-keeping antibiotic effect, has suppressed the metabolic process of bacterium, has prolonged the pot-life of fresh food such as vegetables and fruits, has kept flavours in food products and nutritive value, and this all is crucial.
Free metal ion generation complex reaction in the metal ion of complex antimicrobials employing chitin derivativ of the present invention and interpolation and the medical stone, the high efficiency of additive capability that keeps medical stone simultaneously, through the double action of chemistry with physics, obtain being used to prepare the pressed powder with antibacterial and mouldproof of vinyon at last, be applied to prepare the anti-bacterial refreshing plastic master batch, also can further make various plastics more as required.The method that complex antimicrobials of the present invention is applied to prepare master batch is simple, and its fresh-keeping antibacterial and mouldproof of the preservative film of production is effective, is easy to industrial applying.
Embodiment
Below further specify technical scheme of the present invention by specific embodiment, all umbers are weight portion.
The preparation of embodiment 1 medical stone/methylol chitin compound antibacterial powder
Measure the 1L deionized water, add the methylol chitin of 30g sheet, be heated to 80 ℃ while stir, it is dissolved fully, the cooling back becomes clear, viscous solution.Above-mentioned solution and mixed being incorporated in the miniature high-speed agitator of 1kg 2500 purpose medical stones are stirred.Adding the 400g weight percent concentration is 20%CaCl
2Solution is treated its slowly complexing.Filtering solution then, residual filter residue placed 100 ℃ of oven dry after, the Powdered medical stone of crushing screening/methylol chitin complex antimicrobials.
Embodiment 2
The preparation complex antimicrobials: measure the 1L deionized water, add the methylol chitin of 10g sheet, be heated to 80 ℃ while stir, it is dissolved fully, the cooling back becomes clear, viscous solution.Above-mentioned solution and mixed being incorporated in the miniature high-speed agitator of 1kg 2500 purpose medical stones are stirred.Adding the 400g weight percent concentration is 25%CuCl
2Solution is treated its slowly complexing.Filtering solution then, residual filter residue placed 100 ℃ of oven dry after, the Powdered medical stone of crushing screening/methylol chitin complex antimicrobials.
Preparation master batch: with 30 parts of the complex antimicrobials that make, 65 parts of LDPE 1F7B, SiO
25 parts, KMnO
42 parts, 0.5 part of Arlacel-20,2 parts in paraffin (50～80 ℃ of fusing points) is kneaded into the mud shape, discharging in homogenizer; What make kneads material in the dual-screw-stem machine of φ 25, and extruding pelletization makes fresh-keeping antibacterial matrices.The temperature of extruder is set at: 130,150,160,170, and 170 ℃; Rotating speed 40r/min.
The antibacterial effect of check master batch: make with 6 parts of fresh-keeping antibacterial matrices, after LDPE100 part is mixed, in extruding the blown film unit (the same double screw extruder adds the blown film device), temperature design 140,170,180,185,185 ℃.It is the film of 20 μ m that blown film becomes thickness, through food hygiene, antibiotic relevant mark with mildew-resistant evaluation test (GB9687-1998, GB/T2591-2003, ASTM G21-96).Obtain following result:
(1) GB9687-1998: meet used for packing foods polyethylene formation product sanitary standard.
(2) GB/T2591-2003: bacteriostasis rate 79.3%
(3) ASTM G21-96: mildew-resistant grade 0-no mildew
Embodiment 3
The preparation complex antimicrobials: measure the 1L deionized water, add the methylol chitin of 100g sheet, be heated to 80 ℃ while stir, it is dissolved fully, the cooling back becomes clear, viscous solution.Above-mentioned solution and mixed being incorporated in the miniature high-speed agitator of 1.5kg 2500 purpose medical stones are stirred.Adding the 300g weight percent concentration is 15%AlCl
3Solution is treated its slowly complexing.Filtering solution then, residual filter residue placed 100 ℃ of oven dry after, the Powdered medical stone of crushing screening/methylol chitin complex antimicrobials.
The preparation master batch: the medical stone that makes/methylol chitin compound antibacterial powder, get 30 parts equally, 65 parts of LDPE1F7B, SiO
25 parts, KMnO
43 parts, 0.5 part of Arlacel-20,2 parts in paraffin (50～80 ℃ of fusing points) is kneaded into the mud shape, discharging in homogenizer; What make kneads material in the dual-screw-stem machine of φ 25, and extruding pelletization makes fresh-keeping antibacterial matrices.The temperature of extruder is set at: 130,150,160,170, and 170 ℃; Rotating speed 40r/min.
The antibacterial effect of check master batch: the master batch that makes under the condition of embodiment 2 with the LDPE blowfilm shaping, through food hygiene, the antibiotic relevant result who marks evaluation test (GB9687-1998, GB/T2591-2003, ASTM G21-96) be with mildew-resistant:
(1) GB9687-1998: meet used for packing foods polyethylene formation product sanitary standard.
(2) GB/T2591-2003: bacteriostasis rate 84.1%
(3) ASTM G21-96: mildew-resistant grade 0-no mildew
Embodiment 4
Preparation master batch: get 20 parts of the complex antimicrobials that embodiment 1 makes, 50 parts of LDPE 1F7B, SiO
27 parts, KMnO
45 parts, 0.1 part of Arlacel-20,1 part in paraffin (50～80 ℃ of fusing points) is kneaded into the mud shape, discharging in homogenizer; What make kneads material in the dual-screw-stem machine of φ 25, and extruding pelletization makes fresh-keeping antibacterial matrices.The temperature of extruder is set at: 130,150,160,170, and 170 ℃; Rotating speed 40r/min.
The antibacterial effect of check master batch: the master batch that makes under the condition of embodiment 2 with the LDPE blowfilm shaping, through food hygiene, the antibiotic relevant result who marks evaluation test (GB9687-1998, GB/T2591-2003, ASTM G21-96) be with mildew-resistant:
(1) GB9687-1998: meet used for packing foods polyethylene formation product sanitary standard.
(2) GB/T2591-2003: bacteriostasis rate 85.6%
(3) ASTM G21-96: mildew-resistant grade 0-no mildew
Embodiment 5
The preparation complex antimicrobials: measure the 1L deionized water, add the methylol chitin of 80g sheet, be heated to 80 ℃ while stir, it is dissolved fully, the cooling back becomes clear, viscous solution.Above-mentioned solution and mixed being incorporated in the miniature high-speed agitator of 1.5kg 2500 purpose medical stones are stirred.Adding the 500g weight percent concentration is 30%ZnCl
2Solution is treated its slowly complexing.Filtering solution then, residual filter residue placed 100 ℃ of oven dry after, the Powdered medical stone of crushing screening/methylol chitin complex antimicrobials.
The preparation master batch: the medical stone that makes/methylol chitin compound antibacterial powder is got 50 parts, 80 parts of LDPE 1F7B, SiO
210 parts, KMnO
45 parts, 0.3 part of Arlacel-20,1 part in paraffin (50～80 ℃ of fusing points) is kneaded into the mud shape, discharging in homogenizer; What make kneads material in the dual-screw-stem machine of φ 25, and extruding pelletization makes fresh-keeping antibacterial matrices.The temperature of extruder is set at: 130,150,160,170, and 170 ℃; Rotating speed 40r/min.
The antibacterial effect of check master batch: the master batch that makes under the condition of embodiment 2 with the LDPE blowfilm shaping, through food hygiene, the antibiotic relevant result who marks evaluation test (GB9687-1998, GB/T2591-2003, ASTM G21-96) be with mildew-resistant:
(1) GB9687-1998: meet used for packing foods polyethylene formation product sanitary standard.
(2) GB/T2591-2003: bacteriostasis rate 80.9%
(3) ASTM G21-96: mildew-resistant grade 0-no mildew
Embodiment 6
Method and proportioning with reference to embodiment 1 change complexation of metal ions solution into BaCl
2Make compound antibacterial powder, and then use and embodiment 2 identical methods make master batch, again through identical with embodiment 2 condition and LDPE blowfilm shaping, be through food hygiene, the antibiotic relevant result who marks evaluation test (GB9687-1998, GB/T2591-2003, ASTM G21-96) with mildew-resistant:
(1) GB9687-1998: meet used for packing foods polyethylene formation product sanitary standard.
(2) GB/T2591-2003: bacteriostasis rate 86.5%
(3) ASTM G21-96: mildew-resistant grade 0-no mildew
Claims (6)
1. a complex antimicrobials is formed by chitin derivativ, medical stone and complexing of metal ion, and described metal ion is Ca
2+, Zn
2+, Cu
2+, Ba
2+Or Al
3+
2. complex antimicrobials as claimed in claim 1 is characterized in that described chitin derivativ is selected from carboxymethyl chitin, carboxyethyl chitin, carboxymethyl ethyl chitin, carboxylic propyl group chitin, carboxylic butyl chitin, CMC, carboxyetbyl chitosan, carboxymethyl ethyl chitosan or carboxylic butyl shitosan.
3. the preparation method of the described complex antimicrobials of claim 1 is:
The preparation weight percent concentration is 1%～10% the chitin derivativ aqueous solution, press the chitin derivativ aqueous solution again: the medical stone quality is than adding medical stone for 1:1～1.5, mixing, add an amount of weight percent concentration then and be 15～30% saturated metal ion solution, filter after the complexing, filter residue and drying promptly.
4. the application of the described complex antimicrobials of claim 1 in the fresh-keeping antibiotic plastic of preparation.
5. application as claimed in claim 4 is characterized in that described application in the fresh-keeping antibiotic plastic of preparation is that described complex antimicrobials is used to prepare master batch.
6. application as claimed in claim 5 is characterized in that describedly complex antimicrobials is used to prepare master batch is: with 20～50 weight portion complex antimicrobials, and 50～80 weight portion low density polyethylene (LDPE) 1F7B, 5～10 weight portion SiO
2, 2～5 weight portion KMnO
4, 0.1～0.5 weight portion Arlacel-20,1～2 weight portion fusing point is 50～80 ℃ a paraffin, makes the material of kneading; The material of kneading makes master batch through extruding pelletization; Extrusion temperature is: 130 ℃～170 ℃.
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| CN 200910036823 CN101473847B (en) | 2009-01-20 | 2009-01-20 | Composite anti-bacteria agent as well as preparation method and use thereof |
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| CN101473847B CN101473847B (en) | 2013-01-02 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408628A (en) * | 2011-09-21 | 2012-04-11 | 浙江金海环境技术股份有限公司 | Chitin-containing polymer master batch, air filtering net monofilament, its preparation method and application |
| CN103271413A (en) * | 2013-05-08 | 2013-09-04 | 南京年吉冷冻食品有限公司 | Novel bean curd preservative compounding method |
| CN103734872A (en) * | 2013-12-25 | 2014-04-23 | 吴江华诚复合材料科技有限公司 | Compounding method for novel bean curd preservative |
| CN111378200A (en) * | 2020-04-22 | 2020-07-07 | 武汉大学 | Carboxymethyl chitin porous granular material, preparation method and application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011488A (en) * | 2017-05-16 | 2017-08-04 | 马嘉 | A kind of preparation and application of NEW TYPE OF COMPOSITE antiseptic and its master batch |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294144A (en) * | 2000-11-14 | 2001-05-09 | 上海博纳科技发展有限公司 | Mother particles of antibacterial plastics and its application in preparing antibacterial plastic products |
| CN100360035C (en) * | 2005-04-30 | 2008-01-09 | 武汉大学 | Preparation method of chitin/zinc compound bactericide |
| CN1709062A (en) * | 2005-06-10 | 2005-12-21 | 中国乐凯胶片集团公司 | Medical stone inorganic antibacterial agent and its preparing method |
-
2009
- 2009-01-20 CN CN 200910036823 patent/CN101473847B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408628A (en) * | 2011-09-21 | 2012-04-11 | 浙江金海环境技术股份有限公司 | Chitin-containing polymer master batch, air filtering net monofilament, its preparation method and application |
| CN103271413A (en) * | 2013-05-08 | 2013-09-04 | 南京年吉冷冻食品有限公司 | Novel bean curd preservative compounding method |
| CN103734872A (en) * | 2013-12-25 | 2014-04-23 | 吴江华诚复合材料科技有限公司 | Compounding method for novel bean curd preservative |
| CN111378200A (en) * | 2020-04-22 | 2020-07-07 | 武汉大学 | Carboxymethyl chitin porous granular material, preparation method and application |
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| CN101473847B (en) | 2013-01-02 |
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