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CN101440194A - Thermoset amino resin antibacterial and sterilizing material, and preparation and use thereof - Google Patents

Thermoset amino resin antibacterial and sterilizing material, and preparation and use thereof Download PDF

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Publication number
CN101440194A
CN101440194A CNA2008101344792A CN200810134479A CN101440194A CN 101440194 A CN101440194 A CN 101440194A CN A2008101344792 A CNA2008101344792 A CN A2008101344792A CN 200810134479 A CN200810134479 A CN 200810134479A CN 101440194 A CN101440194 A CN 101440194A
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amino resin
weight part
thermoset amino
antibacterial sterilization
sterilization material
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CNA2008101344792A
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Inventor
卢炳坤
别良峰
高政选
贺玉玲
卢亚南
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Abstract

The invention discloses a thermosetting aminoresin antibacterial material, a preparation method and application thereof. The thermosetting aminoresin antibacterial material comprises the following compositions: 20 to 70 weight portions of thermosetting aminoresin, 0.1 to 8 portions of antibacterial agent, 20 to 70 weight portions of filler or degradable plant powder materials, and 0.1 to 5 weight portions of auxiliary agent. The product has continuous, long-term and mighty broad spectrum sterilization and inhibition functions on more than 300 varieties of harmful microorganisms such as Aspergillus flavus, Pseudomonas aeruginosa, Staphylococcus aureus, colibacillus, Rhodococcus rhodochrous, Candida albicans and budded colibacillus, and finished products have the sanitary and self-cleaning function. As measured by a national authoritative institution, the thermosetting aminoresin antibacterial material is safe and nontoxic to human body and accords with the GB9690-1988 sanitary standard issued by the country. The antibacterial effect of the product accords with the QB/T2591-2003 standard issued by the country and simultaneously accords with the international antibacterial effect standard.

Description

Thermoset amino resin antibacterial, sterilization material and its production and application
Technical field
The present invention relates to a kind of antibiotic, sterilization material and its production and application, more particularly relate to a kind of thermoset amino resin antibacterial, sterilization material and its production and application.
Background technology
People contact one of plastic tableware, chopsticks, article that the drinking-water apparatus is maximum in daily life, yet frosting often is infected with and the morbific bacterium of multiple communicate illness or condition is arranged now, causes very big prestige to assist to people are healthy.Chopsticks also cause the predation exploitation to green environment with wood and destroy.
By the patent name that the applicant declares be in December, 2000: have the problem of all many-sides in " production method of antibacterial plastics for food or beverage containers ", have and get the just mistake of materials aspect, and actual can't processing.
Summary of the invention
One of purpose of the present invention provides a kind of thermoset amino resin antibacterial sterilization material and its production and application.
This and other purpose of the present invention will and be described by following detailed description and further launch and set forth.
Thermoset amino resin antibacterial sterilization material of the present invention is grouped into by following one-tenth:
The thermoset amino resin of 20-70 weight part, 0.1-8 weight part antiseptic-germicide,
20-70 weight part filler or plant degradation powder material, 0.1-5 weight part auxiliary agent.
Further, thermoset amino resin antibacterial sterilization material of the present invention is grouped into by following one-tenth:
The thermoset amino resin of 30-60 weight part, 0.5-5 weight part antiseptic-germicide,
30-60 weight part filler or plant degradation powder material, 0.5-5 weight part auxiliary agent.
What can select is that thermoset amino resin antibacterial sterilization material of the present invention is grouped into by following one-tenth:
The thermoset amino resin of 30-60 weight part, 0.5-5 weight part antiseptic-germicide,
30-60 weight part filler or plant degradation powder material, 1.0-5 weight part auxiliary agent
In thermoset amino resin antibacterial sterilization material of the present invention, described thermoset amino resin is aminoresin or cyanurotriamide modified unsaturated polyester, or thermoset amino resin (as: production of Puyang melamine plastics factory), melamine formaldehyde resin (as: Tianan Enterprise Group, Puyang's production), the resin of etherified urea urea formaldehyde, stupid bird amine formaldehyde resin and their copolycondensations, aminoresin CZ-T, the CZ-N of import, amino Lacquer finish powder, melamine modification unsaturated polyester, (as: production of chemical industry three factories of Yanshan Petrochemical company) etc.Described filler or plant degradation powder material are alpha-cellulose, wood powder or mineral filler such as glass fibre and mica.Described antiseptic-germicide is pure natural Sorbic Acid extract, silver zeolite, silver-colored granulated glass sphere, silver-colored silica gel, polypyridine, phosphoric acid titanium salt, active carbon of silver or polystyrene hexanoyl urea, and the antiseptic-germicide ability is high temperature more than 90 ℃, antibiotic, sterilization effect reaches 〉=and more than 99.9%.Described auxiliary agent is coupling agent, solidifying agent, tinting material, lubricant, stablizer, softening agent or promotor.Described promotor is Zinic stearas, calcium stearate, aluminum stearate, stearic acid fat, stearic acid or glyceride.
The preparation method of thermoset amino resin antibacterial sterilization material of the present invention, can adopt the method for molding, comprise above-mentioned thermoset amino resin antibacterial sterilization material preheating, temperature is controlled at 60 ℃-140 ℃, time is 1-5 minute, then the raw material of preheating being put into mould, is the antibiotic and sterilizing finished product through heating, pressurization, curing molding.
The preparation method of thermoset amino resin antibacterial sterilization material of the present invention, can adopt injection molding method, comprise above-mentioned thermoset amino resin antibacterial sterilization material is added in the barrel, by barrel being heated outward and utilizing screw rod when rotation to produce and the material heat of friction, it is carried out inside and outside heating, make its fusion and produce flowability, under the crunch of screw rod, thick gelationus melting charge by nozzle, is injected the cast gate of mould, runner also is full of die cavity, 60 ℃-150 ℃ of temperature controls, under pressure 80-260Mpa, be cured reaction, after the 0.3min-6min pressurize, i.e. curing molding.
The purposes of thermoset amino resin antibacterial sterilization material of the present invention can be used as tableware or food uses base-material.
Antibiotic and sterilizing principle of the present invention is: the high speed ion that is rich in the antibiotic bactericide powder contacts little pathogeny biochron, after positively charged antibiotic and sterilizing composition touches electronegative microorganism cells, act on by the Coulomb's force, absorption mutually, produce oligodynamic effect, make both mortise, cause positively charged ion to puncture cytolemma effectively, enter in the pathogeny microorganism and sulfydryl on the microorganism internal protein, amino reacts, make the structure deteriorate of pathogeny microprotein, the pathogeny protein denaturation causes the pathogeny microorganism to breathe, metabolism and breeding, until death, reach the propagable effect of no pathogeny bacterium.
When using the sterilant powder, conscientiously select according to the physicochemical property that uses base-material, make it not only have above-mentioned functions but also meet the photocatalytic activity oxygen mechanism of alleviating principle.
The present invention compares with the plastic tableware that tradition is used, because after one of above-mentioned polymkeric substance and antiseptic-germicide powder obtain outstanding compatibility processing, generation is to the blue positive bacteria of benzene, Aspergillus flavus, yeast, intestinal bacteria, klebsiella pneumoniae, subtilis, streptococcus aureus, the mould of anti-the methoxy, Pseudomonas aeruginosa, proteus vulgaris, the short bacterium of flax, streptomycete, fungi, gamboge is folded coccus, Candida albicans, aspergillus niger, flavus, terreus, Aureobasidium pullulans, paecilomyces varioti, the rope form chactomium globosum, the green ochre mould, the rope mould, Penicillium citrinum, Penicillium islandicum, the handle broom is mould, Mucor racemosus, green gloomy mould, Aspergillus nidulans, more than 300 kind of pathogenic microorganism of prunosus red coccus has intensive to suppress and killing action.Simultaneously, the sustainable secular antibiotic and sterilizing of inorganic active component.Can not influence the physicals of tableware, more can not work the mischief human body.Only need clear water to clean after tableware uses, the sterilizing works that need not to carry out disinfection again just can reach cleaning, health.
The present invention is made with wet production by components such as thermoset amino resin, filler or plant degradation powder material (commercially available prod), antibiotic bactericide powder, coupling agent, solidifying agent, tinting material, lubricant, stablizer, softening agent.1, its thermosetting resin adopts the more shallow polycondensate of level of response, and this moment, resin viscosity was little, was convenient to flood filler, and can possess in the long production cycle, carried out still having suitable La Xige flowability after the drying.2, filler is: secondly alpha-cellulose is wood powder or mineral filler (as glass fibre, mica etc.).Used alpha-cellulose is the purified Mierocrystalline cellulose of bleaching, and it is mobile big that consumption is crossed minimodel material powder, and finished product intensity is low, otherwise when consumption was too much, model material powder flowability was little, and product surface is rough, and water tolerance reduces.3, the antibiotic bactericide powder not only needs to have anti-microbial property efficient, wide spectrum, and the antibiotic and sterilizing persistence is good, keeps thermosetting molding compound powder antibiotic and sterilizing for a long time, and nontoxic free from extraneous odour of while is to goods and environmental nonpollution.And just right with the good compatibleness of thermoset ammonia resin compatible, physical properties of articles there is not detrimentally affect, colour stable is being preserved and the use nondiscoloration.Fully take into account in thermosetting molding compound powder, cyanurotriamide modified unsaturated polyester, the PBT course of processing influence of severe condition such as high heat, high pressure, strong shearing to the sterilant powder, requirement is not decomposed in process of manufacture, is never degenerated.It is pure natural Sorbic Acid extract that the present invention adopts the antibiotic bactericide powder more than two kinds.Inorganic antiseptic is silver zeolite, silver-colored granulated glass sphere, silver-colored silica gel.Polymer Synthesizing antiseptic-germicide powder is a polypyridine.Usage quantity is the 0.1-8% of material total amount, and controlled temperature is at 60 ℃-90 ℃, and pH value is controlled: 5-11; Normal conditions are mixing, knead or compound process in add.4, solidifying agent requires to have certain latent, and what the present invention used is phthalic acid or phenylformic acid.5, tinting material is to use the strong pigment of tinting strength, must be uniformly dispersed.Nondiscoloration when processing high temperature and secular sun exposure more can not separated out from goods.Consumption is the 0.01-0.6 weight part of inventory.6, lubricant can improve the flowability of material when compacting, injection molding, helps goods to deviate from from mould, and lubricant commonly used is a Metallic stearates, as calcium, aluminium, magnesium, hexamethylene fat, and the 0.1-2% of inventory during its consumption.
The present invention adopts aminoresin, if the mol ratio trimeric cyanamide: the weight part of formaldehyde=1:(1.5-3.8).Condition is: 65 ℃-98 ℃ of temperature, pH value is controlled at 5.5-10, carries out the reaction of addition, forms melamine methylol.The viscosity controller 10-50S/25 of resin solution ℃, add the fiber or the glass fibre of bleaching, add antibiotic, sterilant powder and other auxiliary agents again and knead, the time is 0.5-4 hour.Blowing enters the drying machine oven dry, and sieve series becomes thermoset antibiotic and sterilizing model material powder KAY (production of Henan Province placanticline shaft coupling factory) behind ball mill grinding then
The compression moulding of antibiotic and sterilizing tableware, chopsticks, drinking-water apparatus is to obtain amino antibiotic powder (KAY) preheating of thermoset, can adopt the method for infrared heating or ratio-frequency heating to carry out, and temperature is controlled at 60 ℃-140 ℃.Time decides on its degree of drying.Then the raw material of preheating being put into mould, is the antibiotic and sterilizing finished product through heating, pressurization, curing molding.
To the goods of different shaped shape, different although their employed starting material are formed, the principle and the process of its compression moulding are basic identical.The principal feature of moulding process is: 1. be not only resin flows in the process of mold pressing, and antibiotic bactericide powder and filler are full of each position of die cavity also with resin flows; 2. each evacuation time is 2S-25S; 3. control 30 seconds to 15 minutes usually set time; 4. die temperature is controlled at 120 ℃-195 ℃; 5. bleeding is wanted rapidly, and one fixes on when raw material still is in plastic state and finishes, otherwise raw material sclerosis back influences product properties and apparent mass.
Injection thermoset antibiotic and sterilizing tableware forming principle is: the antibiotic raw material (KAY) that will obtain adds in the barrel, by barrel being heated outward and utilizing screw rod when rotation to produce and the material heat of friction, it is carried out inside and outside heating, make its fusion and produce flowability, under the crunch of screw rod, thick gelationus melting charge is passed through nozzle, inject cast gate, the runner of mould and be full of die cavity, 60 ℃-190 ℃ of temperature controls, under pressure 80-260Mpa, be cured reaction, after for some time pressurize, i.e. curing molding.Open injection molding then, promptly obtain antibiotic and sterilizing tableware, chopsticks, drinking-water apparatus.
With injection molding or two kinds of modes of production of compression moulding, require different to the starting material physicochemical property, because thermoset powder, amino modified unsaturated polyester mould powder and PBT are under certain temperature and high pressure and the polymerization of antibiotic and sterilizing pulvis compatibility, their polycondensation and curing performance all have reduction in various degree.So must before injection molding, use softening agent to strengthen the snappiness and the flowability of injection material; Use a small amount of curing catalyst, impel antibiotic and sterilizing material fast setting under the hot pressing condition in die cavity, its shaping cycle is shortened.Solidifying agent uses magnesium oxide usually, the 0.1-3.0 weight part of consumption material.
The base-material that is used to make tableware can be a thermosetting molding compound material powder; Unsaturated polyester class, aminoresin class, Synolac class, a kind of by the superior principle of its compatibility attribute in the materials such as aralkyl ethers selects following a kind or several for use: quaternary ammonium salt, chitosan, polypyridine, silver zeolite, active carbon of silver, thiazoles.Antimicrobial nano material etc.Its manufacture craft is: add an amount of antiseptic-germicide powder in the base-material production process; Also can be directly in raw material, add an amount of antibiotic powder, through polyreaction, composite, dehydration, dry, make powder; Be processed into the antibiotic and sterilizing tableware by hydropress or injection.
Product of the present invention all has lasting long-acting to more than 300 kind of harmful microorganism such as flavus, Pseudomonas aeruginosa, streptococcus aureus, colibacillus, prunosus red coccus, Candida albicans, the Da Lan bacillus that sprouts, wide spectrum, strong disinfecting and restraining effect, its finished product has the health self-cleaning function.Simultaneously abundant, the bright in color of tableware pattern, pollution-free, anti-boiling water, imitative porcelain effect are very true to nature, and this propagates with regard to fruitful avoided bacterium and disease ground.Detect the human body safety non-toxic through national authority mechanism, meet the promulgation GB9690-1988 of country hygienic standard.Its goods antibacterial effect meets QB/T2591-2003 standard promulgated by the ministries or commissions of the Central Government, meets the standard of international antibacterial effect simultaneously.
The all raw material of Shi Yonging etc. all is conventional uses in the present invention, can buy from market.In the present invention, refer in particular to as non-, all amount, per-cents are weight unit.
Below in conjunction with embodiment the present invention is carried out concrete description.As known by the technical knowledge, the present invention can realize by other the embodiment that does not break away from its spirit or essential feature.Therefore, following embodiment with regard to each side, all just illustrates, and is not only.All within the scope of the present invention or the change that is equal in the scope of the present invention all be included in the invention.
Description of drawings
Fig. 1 is the compression moulding process flow sheet;
Fig. 2 is the injection molding technique schema.
Embodiment
Embodiment 1
Take by weighing each raw material by following weight ratio:
The thermoset amino resin of 50 weight parts (production of Puyang, Henan Province melamine plastics factory), 3 weight part antiseptic-germicides (pure natural Sorbic Acid extract), 45 weight part alpha-celluloses, 2 weight part auxiliary agents (coupling agent of conventional plastic working use, solidifying agent, tinting material, lubricant, stablizer, softening agent etc.)
Above-mentioned raw materials is mixed, stir, oven dry is 0.5 hour under 50 ℃ of-110 ℃ of environment, makes anti-biotic material, is processed into the antibiotic and sterilizing tableware through the hydropress injector again.
Embodiment 2
Take by weighing each raw material by following weight ratio:
The melamine formaldehyde resin of 47 weight parts (Tianan Enterprise Group, Puyang's production), 2 weight part antiseptic-germicides (silver zeolite), 57 weight part wood powders, 3 weight part auxiliary agents (coupling agent of conventional plastic working use, solidifying agent, tinting material, lubricant, stablizer, softening agent etc.)
Above-mentioned raw materials is mixed, stir, oven dry is 1.0 hours under 50 ℃ of-110 ℃ of environment, makes anti-biotic material, is processed into the antibiotic and sterilizing tableware through the hydropress injector again.
Embodiment 3
Take by weighing each raw material by following weight ratio:
The etherified urea urea formaldehyde of 50 weight parts, 3.5 weight part antiseptic-germicide (polypyridine), 42 weight part plant degradation powder materials (Tianan Enterprise Group, Puyang's production), 4.5 weight part auxiliary agents (coupling agent of conventional plastic working use, solidifying agent, tinting material, lubricant, stablizer, softening agent etc.)
Above-mentioned raw materials is mixed, stir, oven dry is 1.2 hours under 70 ℃ of ℃ of environment, makes anti-biotic material, is processed into the antibiotic and sterilizing tableware through the hydropress injector again.
Embodiment 4
Take by weighing each raw material by following weight ratio:
The thermoset amino resin of 35 weight parts (production of Puyang, Henan Province melamine plastics factory), 4.5 weight part antiseptic-germicide (polypyridine), 56 weight part plant degradation powder materials (Tianan Enterprise Group, Puyang's production), 4.5 weight part auxiliary agents (coupling agent of conventional plastic working use, solidifying agent, tinting material, lubricant, stablizer, softening agent etc.)
Resin in the base-material production process and filler reaction, kneading or polymerization workshop section add antiseptic-germicide, make anti-biotic material, are processed into antibiotic tableware through hydropress or injector.
Embodiment 5
Take by weighing each raw material by following weight ratio:
The etherified urea urea formaldehyde of 45 weight parts, 3.5 weight part antiseptic-germicide (silver-colored silica gel), 48 weight part plant degradation powder materials (Tianan Enterprise Group, Puyang's production), 3.5 weight part auxiliary agents (coupling agent of conventional plastic working use, solidifying agent, tinting material, lubricant, stablizer, softening agent etc.)
With amino antibiotic powder (KAY) preheating of the above-mentioned thermoset that obtains, can adopt the method for infrared heating or ratio-frequency heating to carry out, temperature is controlled at 60 ℃-140 ℃.Time is 0.5 hour.Then the raw material of preheating being put into mould, is the antibiotic and sterilizing finished product through heating, pressurization, curing molding.
Its technical process is: raw material, drying and preheating, mold closing, 1 exhaust, applique, curing, Lacquer finish, 2 exhausts, the demoulding, cooling, arrangement, polishing and finished products.Antibiotic bactericide powder and filler are full of each position of die cavity with resin flows.Each evacuation time is 2S-25S, controls 30 seconds to 15 minutes set time usually.Die temperature is controlled at 120 ℃-195 ℃.Bleeding is wanted rapidly, and one fixes on when raw material still is in plastic state and finishes, otherwise raw material sclerosis back influences product properties and apparent mass.
Embodiment 6
Take by weighing each raw material by following weight ratio:
The etherified urea urea formaldehyde of 51 weight parts, 3.0 weight part antiseptic-germicide (silver-colored silica gel), 44 weight part plant degradation powder materials (Tianan Enterprise Group, Puyang's production), 2.0 weight part auxiliary agents (coupling agent of conventional plastic working use, solidifying agent, tinting material, lubricant, stablizer, softening agent etc.)
The above-mentioned raw material that obtains (KAY) is added in the barrel, by barrel being heated outward and utilizing screw rod when rotation to produce and the material heat of friction, it is carried out inside and outside heating, make its fusion and produce flowability, under the crunch of screw rod, thick gelationus melting charge by nozzle, is injected cast gate, the runner of mould and is full of die cavity, 100 ℃-190 ℃ of temperature controls, under pressure 90-260Mpa, be cured reaction, after for some time pressurize, i.e. curing molding.Open injection molding then, promptly obtain antibiotic and sterilizing tableware, chopsticks, drinking-water apparatus.
The injection molding technique flow process is: loading hopper, barrel charging, preformed, plasticizing metering, matched moulds, injection, exhaust, applique, pressurize, curing reaction, die sinking, pushing-off product and cleaning mould.

Claims (10)

1, a kind of thermoset amino resin antibacterial sterilization material is characterized in that being grouped into by following one-tenth:
The thermoset amino resin of 20-70 weight part, 0.1-8 weight part antiseptic-germicide,
20-70 weight part filler or plant degradation powder material, 0.1-5 weight part auxiliary agent.
2, thermoset amino resin antibacterial sterilization material according to claim 1 is characterized in that being grouped into by following one-tenth:
The thermoset amino resin of 30-60 weight part, 0.5-5 weight part antiseptic-germicide,
30-60 weight part filler or plant degradation powder material, 0.5-5 weight part auxiliary agent.
3, thermoset amino resin antibacterial sterilization material according to claim 1 is characterized in that being grouped into by following one-tenth:
The thermoset amino resin of 30-60 weight part, 0.5-5 weight part antiseptic-germicide,
30-60 weight part filler or plant degradation powder material, 1.0-5 weight part auxiliary agent
4,, it is characterized in that described thermoset amino resin is aminoresin or cyanurotriamide modified unsaturated polyester according to the described thermoset amino resin antibacterial sterilization material of one of claim 1-3.
5, according to the described thermoset amino resin antibacterial sterilization material of one of claim 1-3, it is characterized in that described antiseptic-germicide is pure natural Sorbic Acid extract, inorganic antiseptic active carbon of silver, phosphoric acid titanium salt, silver zeolite, silver-colored granulated glass sphere, silver-colored silica gel or polystyrene hexanoyl urea.
6,, it is characterized in that described filler is alpha-cellulose, wood powder or mineral filler such as glass fibre and mica according to the described thermoset amino resin antibacterial sterilization material of one of claim 1-3.
7,, it is characterized in that described auxiliary agent is coupling agent, solidifying agent, tinting material, lubricant, stablizer, softening agent or promotor according to the described thermoset amino resin antibacterial sterilization material of one of claim 1-3.
8, according to the preparation method of the described thermoset amino resin antibacterial sterilization material of one of claim 1-7, it is characterized in that adopting the method for molding, comprise above-mentioned thermoset amino resin antibacterial sterilization material preheating, temperature is controlled at 60 ℃-140 ℃, time is 1-5 minute, then the raw material of preheating being put into mould, is the antibiotic and sterilizing finished product through heating, pressurization, curing molding.
9, preparation method according to the described thermoset amino resin antibacterial sterilization material of one of claim 1-7, it is characterized in that adopting injection molding method, comprise above-mentioned thermoset amino resin antibacterial sterilization material is added in the barrel, by barrel being heated outward and utilizing screw rod when rotation to produce and the material heat of friction, it is carried out inside and outside heating, make its fusion and produce flowability, under the crunch of screw rod, thick gelationus melting charge by nozzle, is injected the cast gate of mould, runner also is full of die cavity, 60 ℃-150 ℃ of temperature controls, under pressure 80-260Mpa, be cured reaction, after the 0.3min-6min pressurize, i.e. curing molding.
10, according to the purposes of the described thermoset amino resin antibacterial sterilization material of one of claim 1-7, it is characterized in that can be used as tableware or food product pack purposes base-material, the effect of antibiotic and sterilizing is more than 99.9%.
CNA2008101344792A 2008-07-25 2008-07-25 Thermoset amino resin antibacterial and sterilizing material, and preparation and use thereof Pending CN101440194A (en)

Priority Applications (1)

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CNA2008101344792A CN101440194A (en) 2008-07-25 2008-07-25 Thermoset amino resin antibacterial and sterilizing material, and preparation and use thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNA2008101344792A CN101440194A (en) 2008-07-25 2008-07-25 Thermoset amino resin antibacterial and sterilizing material, and preparation and use thereof

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CN101440194A true CN101440194A (en) 2009-05-27

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103275507A (en) * 2013-06-21 2013-09-04 苏州新区特氟龙塑料制品厂 Anti-bacterial plastic
CN103937153A (en) * 2014-04-01 2014-07-23 常州乔尔塑料有限公司 Broad-spectrum efficient antibacterial amino molding material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103275507A (en) * 2013-06-21 2013-09-04 苏州新区特氟龙塑料制品厂 Anti-bacterial plastic
CN103937153A (en) * 2014-04-01 2014-07-23 常州乔尔塑料有限公司 Broad-spectrum efficient antibacterial amino molding material
CN103937153B (en) * 2014-04-01 2016-03-30 常州乔尔塑料有限公司 The antibacterial amino film plastics of a kind of broad-spectrum high efficacy

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Open date: 20090527