CN106674600A - Preparation method of chitosan-coated heavy calcium carbonate anti-microbial filler for breathable film - Google Patents
Preparation method of chitosan-coated heavy calcium carbonate anti-microbial filler for breathable film Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/26—Carbonates; Bicarbonates
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Abstract
The invention discloses a preparation method of a chitosan-coated heavy calcium carbonate anti-microbial filler for a breathable film. The preparation method mainly comprises the following steps of crushing, homogenizing, grinding, drying and modifying, and has the beneficial effects that by doping chitosan during a production process, a certain anti-microbial performance is endowed to composite powder; meanwhile, a hydrophobic property of the chitosan is beneficial for surface modification of calcium carbonate powder, so that the prepared calcium carbonate composite powder is good in surface sphericity, and uniform in particle size distribution. The preparation method provided by the invention is simple and convenient in technological operation, low in cost, and suitable for industrial large-scale production.
Description
Technical field
The invention belongs to nonmetallic mineral deep processing and utilization, composite and field of functional materials, and in particular to Yi Zhongtou
The air film preparation method of Chitosan-coated ground calcium carbonate antibacterial filler.
Background technology
With social progress and the improvement of people's living standards, in daily life, medical treatment, special industrial protection field, one
The usage amount and use range of secondary property product progressively expands, and in the sales volume of China's disposable product in 2013 30000000000 have been reached
Unit.People propose higher and higher requirement to the comfort of disposable product, and the breathability of disposable product is directly determined
Article made to order comfort.Most disposable products are required for using plastic film material, traditional plastic sheeting in a large number
It is air-locked, the breathability for how easily improving conventional plastic thin film is problem demanding prompt solution.By in conventional plastic
Add rigid function filler in thin film preparation process and make laminated film, then Jing longitudinal directions or biaxial tension obtain answering with micropore
It is the method for improving plastic sheeting breathability modal at present to close thin film, and this composite plastic film with micro-porous permeable is referred to as
Ventilated membrane.
Such ventilated membrane theoretical foundation is laminated film polymer and rigid function filler circle under appropriate external force effect
Face is peeled off, and polymer extends to form the micropore for running through.The pore structure for mutually running through allows small molecule gaseous material to pass through（Such as water
Steam, air etc.）, but liquid cannot pass through such micropore due to surface tension effects, be consequently formed with saturating
The fluid-tight barriers function thin film of gas.In order to meet use requirement and hygienic requirements, thin film strength and surface property can not have
Too big change, particularly can not introduce poisonous and hazardous chemical substance when laminated film is prepared.Based on this, to laminated film system
Filler used in standby just proposes at a relatively high prescription, on the market common filler, such as ground calcium carbonate, Pulvis Talci, weight
Spar etc. can not all meet the prescription of ventilated membrane.
Had the following problems with traditional heavy calcium carbonate filling manufacture ventilated membrane：
1. because particle diameter distribution extensively causes the composite membrane low intensity of preparation, use requirement is not reached, granule has obvious corner angle, system
Standby composite membrane can stimulate skin；
2. the composite membrane for preparing can form a large amount of pinprick defects during stretching pore-forming, and it is thin that pinprick causes liquid also can pass through
Film；
3. the air penetrability of ventilated membrane made by is unstable, forms the air-locked region in local；
4. filler moves to film surface under stress, makes one layer of tear-away powder body of ventilated membrane surface attachment；
5. the grinding aid that filler is used does not account for toxic, it is impossible to reach the hygienic requirements of ventilated membrane；
6. filler disperses uneven in composite membrane, causes coloured dyeing speckle of ventilated membrane etc. to affect quality.
Shitosan has broad spectrum antibiotic activity, is natural organic polymer antibacterial, to staphylococcus aureuses and greatly
The common bacterias such as enterobacteria have inhibitory action；Simultaneously there is substantial amounts of hydrophobic group on shitosan surface, if by Chitosan-coated in weight
Matter calcium carbonate surface not only can reach certain antibacterial effect, and can play the modified effect in surface, advantageously form
The heavy calcium carbonate powder being evenly distributed.And the preparation of the compound heavy calcium carbonate filling of shitosan not yet reports that inventor is directed to
The deficiency of current heavy calcium carbonate powder filler, problem and defect that particularly traditional triple superphosphate is used in ventilated membrane production, there is provided
A kind of brand-new ground calcium carbonate functional stuffing production preparation scheme.
The content of the invention
First technical problem to be solved by this invention is to provide a kind of ventilated membrane Chitosan-coated ground calcium carbonate
The preparation method of antibacterial filler.The method is comprised the following steps：
It is a, broken：By the marble powder that the marble of calcium carbonate content >=99% is 40~70 μm of diameter；
B, homogenizing, grinding：According to weight than the ︰ 0.001~0.1 of Dali stone powder ︰ water ︰ high molecular surfactant=1 ︰ 0.2~1.5
Three is mixed, alumina ball, corundum ball or zirconium oxide that a diameter of 1~20mm accounts for three's gross weight 30~55% is added
Any one in ball, by the way of agitation grinding, mixing time be 1~5h, mixing speed be 500~6000r/min, 60
~200 mesh are filtrated to get calcium carbonate slurry；It is little that the calcium carbonate slurry dehydration that 60~200 mesh are filtrated to get is concentrated into water content
In 25%, then flow velocity is passed through as 5~60m with the speed of 400~1800kg/h3/ s, temperature is to be atomized in 300~450 DEG C of air-flow
Flash distillation to water content is not more than 1%；
It is c, modified：Reunion powder body is dismissed, and drying to water content is not more than 0.2%, addition accounts for powder body gross weight 1%~5% after being dried
Shitosan, add account for the activator of dry powder gross weight 0.5~2% afterwards, in 110~140 DEG C of fully reactions, cooling is mixed,
Packaging.
Specifically, in above-mentioned preparation method step b, described high molecular surfactant is sodium alginate, carboxymethyl fibre
The plain sodium of dimension, polyphosphate sodium, polyacrylamide, polycarboxylic acids sodium, sodium polyacrylate, sodium lignin sulfonate, Polyethylene Glycol, poly- the third two
At least one in alcohol, polyvinyl alcohol, polyvinylpyrrolidone, TH-904 dispersants or calcium lignosulfonate.
Preferably, the high molecular surfactant is polyphosphate sodium by weight and the mixing of 1 ︰ of sodium polyacrylate 1 institute
, sodium lignin sulfonate and 1 ︰ of polycarboxylic acids sodium 2 mixing gained, TH-904 dispersants and 1 ︰ of calcium lignosulfonate 2 mixing gained or
Any one in polycarboxylic acids sodium and the mixing gained of 2 ︰ of sodium polyacrylate 1.
Specifically, in step c, the chitosan solution is water in mass ratio：Glacial acetic acid：The ︰ 0.01 of shitosan=1 ︰ 0.03~
0.05 mix homogeneously gained.
Specifically, the chitosan solution forms atomized liquid by atomising device, and is uniformly wrapped in the form of spraying
Ground calcium carbonate surface.
Specifically, in above-mentioned preparation method step c, described activator be stearic acid, humic acid, Oleic acid, silicol,
It is calcium stearate, zinc stearate, enuatrol, sodium palmitate, palmitic acid calcium, dodecyl sodium sulfate, ethylene bis stearic acid amide, hard
Fat acid monoglyceride, ethylenediamine, aqueous epoxy resins, epoxy soybean oil, Toluene-2,4-diisocyanate, 4- diisocyanate, many isocyanides of 6- methylene
At least one in acid esters, aluminate coupling agent, titanate coupling agent or silane coupler.
Preferably, in above-mentioned preparation method step c, described activator is stearic acid and the ︰ of zinc stearate 1 by weight
1 mixing gained, calcium stearate and the mixing gained of 1 ︰ of ethylene bis stearic acid amide 1, Oleic acid and the mixing gained of 1 ︰ of stearic acid 1, second two
Amine and 1 ︰ of 6- methylene polyisocyanates 1 mix gained or aluminate coupling agent and stearic acid and mix any in gained by 1 ︰ 2
It is a kind of.
Specifically, it is described also including the additive for accounting for marble weight 0.2~0.8% in above-mentioned preparation method step a
Additive is glycerol or at least one in ethylene glycol.
Second technical problem to be solved by this invention is to provide by a kind of above-mentioned ventilated membrane Chitosan-coated heavy
The ventilated membrane heavy calcium carbonate filling that the preparation method of Calcium Carbonate antibacterial filler is prepared.
Specifically, above-mentioned ventilated membrane heavy calcium carbonate filling, particle diameter：D50=0.5~5 μm, D97≤ 10 μm, diameter is less than
2 μm of particulate accumulation content >=45%；Whiteness >=82；15~60g/100g of oil factor；Sphericity 1.2~1.9；Specific surface area >=
35m2/g；Particle diameter distribution≤1.7, with preferable anti-microbial property.
3rd technical problem to be solved by this invention is to provide a kind of above-mentioned ventilated membrane Chitosan-coated heavy carbon
Breathable films dedicated parent material or breathable films PP Pipe Compound that the preparation method of sour calcium antibacterial filler is prepared.
Product of the present invention has the advantages that：
1st, very well, without corner angle, the composite membrane of preparation will not stimulate skin to the sphericity of calcium carbonate powder of the present invention；
2nd, diameter of particle narrowly distributing of the present invention, when ventilated membrane is prepared, will not form the uneven, needle pore defect of dispersion；
3rd, the present invention is raw materials used harmless, and the incorporation of shitosan makes composite granule have certain antibacterial characteristics, therefore,
The ventilated membrane prepared can be with Long Term Contact human body, the problems such as be effectively prevented bacterium infection；
4th, powder body of the present invention is used in ventilated membrane, and Chitosan-coated effect is good, and powder body is uniformly dispersed, and analysis will not be migrated in use
Go out, will not fall off.
Description of the drawings
Fig. 1 is the bacteriostatic experiment performance map of calcium carbonate powder of the present invention.
Specific embodiment
A kind of ventilated membrane preparation method of Chitosan-coated ground calcium carbonate antibacterial filler, comprises the following steps：
A, by the marble Jing multiple stage crushings of selected calcium carbonate content >=99% to a diameter of 3~10mm, it is meticulous to be readily incorporated it
His impurity, excessive to easily cause grinding efficiency low；Again its dry state is ground to into diameter at 40~75 μm, obtains marble powder；
B, in order to improve grinding efficiency and drying efficiency, add high molecular surfactant, by weight, stone powder ︰ water ︰ is high in Dali
The ︰ 0.001~0.1 of molecular surface active agent=1 ︰ 0.2~1.5 mix three；In order to ventilated membrane calcium carbonate for special use powder body is ground
Into required index and saving milling time, the alumina ceramics that a diameter of 1~20mm accounts for three's gross weight 30~55% is added
Any one in ball, corundum ball or zirconia ball, stir 1~5h, mixing speed be 500~6000r/min, 60~200 mesh
Drainage screen carries out being filtrated to get calcium carbonate slurry；Described high molecular surfactant be sodium alginate, sodium carboxymethyl cellulose,
Polyphosphate sodium, polyacrylamide, polycarboxylic acids sodium, sodium polyacrylate, sodium lignin sulfonate, Polyethylene Glycol, polypropylene glycol, polyethylene
At least one in alcohol, polyvinylpyrrolidone, TH-904 dispersants or calcium lignosulfonate；Calcium carbonate slurry is dehydrated dense
Contracting, the water content for making calcium carbonate slurry is not more than 25%, flow velocity is passed through as 5~60m with the speed of 400~1800kg/h3/ s temperature
It is not more than 1% to water content for atomization flash-evaporation in 300~450 DEG C of air-flows；
C, dismiss reunion powder body, and be not more than 0.2% with infrared drying to water content, addition account for split gross weight 1% after being dried~
5% chitosan solution, wherein described chitosan solution is shitosan powder body is dissolved in acetic acid formation according to 1%~5% ratio
Solution, adds afterwards the activator for accounting for dry powder gross weight 0.5~2% in 110~140 DEG C of fully reactions, and cooling is mixed, and packaging is
Can；Described activator is stearic acid, humic acid, Oleic acid, silicol, calcium stearate, zinc stearate, enuatrol, palmitic acid
Sodium, palmitic acid calcium, dodecyl sodium sulfate, ethylene bis stearic acid amide, stearic acid monoglycerides, ethylenediamine, aqueous epoxy resins,
Epoxy soybean oil, Toluene-2,4-diisocyanate, 4- diisocyanate, 6- methylene polyisocyanates, aluminate coupling agent, titanate coupling agent or
At least one in silane coupler.
Preferably, in above-mentioned preparation method step b, described high molecular surfactant is polyphosphate sodium by weight
With the mixing gained of 1 ︰ of sodium polyacrylate 1, sodium lignin sulfonate and the mixing gained of 1 ︰ of polycarboxylic acids sodium 2, TH-904 dispersants and wooden
Any one in the mixing of 1 ︰ of plain sulfoacid calcium 2 gained or polycarboxylic acids sodium and the mixing gained of 2 ︰ of sodium polyacrylate 1.
Preferably, in above-mentioned preparation method step c, it is 1%~5% that shitosan accounts for the mass ratio of compounded mix, wherein matter
When amount fraction is 5%, the antibacterial effect of obtained composite granule is optimal.
Preferably, in above-mentioned preparation method step c, described activator is stearic acid and the ︰ of zinc stearate 1 by weight
1 mixing gained, calcium stearate and the mixing gained of 1 ︰ of ethylene bis stearic acid amide 1, Oleic acid and the mixing gained of 1 ︰ of stearic acid 1, second two
Amine and 1 ︰ of 6- methylene polyisocyanates 1 mix gained or aluminate coupling agent and stearic acid and mix any in gained by 1 ︰ 2
It is a kind of.
By a kind of above-mentioned preparation method of ventilated membrane Chitosan-coated ground calcium carbonate antibacterial filler prepare it is saturating
Air film heavy calcium carbonate filling.
Specifically, above-mentioned ventilated membrane heavy calcium carbonate filling, particle diameter：D50=0.5~5 μm, D97≤ 10, diameter is less than 2 μ
M particulate accumulation content >=45%；Whiteness >=82；15~60g/100g of oil factor；Sphericity 1.2~1.9；Specific surface area >=35m2/
g；Particle diameter distribution≤1.7, with special anti-microbial property.
It is ventilative that a kind of preparation method of above-mentioned ventilated membrane Chitosan-coated ground calcium carbonate antibacterial filler is prepared
Thin film dedicated parent material or breathable films PP Pipe Compound.
D in product index of the present invention50Quantity statistics mean diameter is pressed in expression；D97Represent the particle size range of 97% powder body；
Oil factor represents the minimum quality of the butyl phthalate required for making 100g powder body agglomerating；Sphericity represents single irregular
The maximum gauge of granule different directions and the ratio of minimum diameter；Specific surface area represents the surface area of whole powder body of Unit Weight；
Particle diameter distribution represents the ratio of the mean diameter and mean diameter by statistic of attribute for counting by weight.
Due to traditional Calcium Carbonate be used for ventilated membrane problem it is many, cause be the reason for these：The particle diameter of traditional calcium carbonate powder
Greatly, sphericity is low, particle diameter distribution is too wide, calcium carbonate surface traditional organic-treating does not reach wanting for composite conjugation
Ask, calcium carbonate powder secondary agglomeration is serious etc..
The present inventor is conventional after many experiments are found using high molecular surfactant and zirconium oxide microballon
Stirring reaches grinding effect；Using two-step method dehydrate, product moisture is less than 0.2 %；Powder surface and activation after depolymerization
Agent is reacted, and at utmost the filler to preparing after powder surface organic-treating can overcome above-mentioned problem, from
And reach good effect.
In order to improve follow-up drying efficiency, the more poorly efficient fruit of amount of water is better；But, amount of water is lower and can have a strong impact on
Grinding efficiency, so being dried and grinding efficiency to take into account, inventor has found to add high molecular surfactant in the feed, both
Can meet and be dried and grinding efficiency, high molecular surfactant can be attached to powder surface, reunion when reduction is dried again
Degree, so as to reach good effect.
The generation of the reunion powder body described in the inventive method is because that raw material particle size is trickle, and dry run can promote granule
Between attract each other, formed cluster of grains, be referred to as reunion powder body；Again because reunion powder body cannot embody the effect and work(of powder body itself
Can, so needing to be dismissed, it is referred to as dismissing reunion powder body.
The activator that the present invention is adopted is the Organic substance with the functional group that chemical reaction can occur with powder surface, this
A little functional groups produce chemical reaction with the group of powder surface, form chemical bond, Organic substance are fixed on into powder surface, so as to carry
The compatibility between high powder body and polymer, when ventilated membrane is prepared, is conducive to disperseing and improving ventilative film strength.
Shitosan described in the inventive method has broad spectrum antibiotic activity, is natural organic polymer antibacterial, raw
The thing compatibility is good, if Chitosan-coated not only can be reached into certain antibacterial effect in ground calcium carbonate surface, and can be with
The modified effect in surface is played, when as ventilated membrane filler poisonous and hazardous chemical substance will not be introduced.Meanwhile, surface has greatly
The hydrophobic group of amount, may advantageously facilitate to form the heavy calcium carbonate powder being evenly distributed.
Embodiment 1
The marble Ore of selected calcium carbonate content >=99%, is broken for being put in ring barreling after the fritter of diameter 3mm（Main frame
Rotating speed 1100r/min, rotation speed of fan 4000r/min）D is obtained in dust-precipitator50For 50 μm of marble powder；
4 tons of pure water is taken, polycarboxylic acids sodium is added（Commercially available ROHM AND HAAS 9400）100kg mix homogeneously in premixing tank, by
Gradually add 6 tons of stepsThe marble powder that obtains simultaneously is stirred continuously, and makes pre- slurry；
3. diameter 1.2mm zirconia ball 800kg, diameter 2.2mm zirconia ball 1200kg, diameter are placed with vertical mixing tank
3.8mm zirconia ball 2000kg, progressively pump into stepThe pre- slurry of system and simultaneously by slow-to-fast turn on agitator, in 1800r/
1.5h is stirred under min mixing speeds；
4. the mixture after stirring is filtered by 100 mesh, leaches agitated medium（It is reusable after cleaning）After coarseparticulate
About 9.3 tons of the calcium carbonate slurry that water content is 35% is obtained, takes centrifuge dehydration to be concentrated into water content the calcium carbonate slurry to be
23%, flow velocity 15m is sprayed into the speed of 45° angle 650kg/h3Atomization is carried out in 350 DEG C of air-flows of/s and moment is evaporated, obtained about
The reunion powder body of 5.9 tons of water content 0.8%；
5. reunion powder body depolymerization 1min in by the high speed depolymerizer that infrared radiation device steady temperature is 135 DEG C, obtains aqueous
The powder body for 0.16% is measured, while adding chitosan solution（Shitosan accounts for the 0% of dry powder gross weight）, the silane of 50kg is added afterwards
Coupling agent（Commercially available KH550）Fully reacted, obtained 5.8 tons of ventilated membrane Chitosan-coated ground calcium carbonate antibacterial filler；
6. ventilated membrane Chitosan-coated ground calcium carbonate antibacterial filler is collected in homogenizing 3min in all mixing tank, temperature by air-flow
Being down to room temperature carries out quantitative package.
The present embodiment gained ventilated membrane is as follows with Chitosan-coated ground calcium carbonate antibacterial filler performance：Particle diameter：D50=2.2μ
M,D97=5.8 μm, diameter is less than 2 μm of particulate accumulation contents 78%；Whiteness 91；Oil factor 32g/100g；Sphericity 1.4；Specific surface
Product 55m2/g；Particle diameter distribution 1.5, with certain antibacterial characteristics.
Embodiment 2
The marble Ore of selected calcium carbonate content >=99%, is broken for being put in ball mill after the fritter of diameter 8mm（Main frame
Rotating speed 600r/min, rotation speed of fan 2000r/min）D is obtained in dust-precipitator50For 40 μm of marble powder；
2.5 tons of pure water is taken, sodium polyacrylate is added（Commercially available molecular weight is more than 10,000）120kg mixes in premixing tank
It is even, it is gradually added into 5.5 tons of stepsThe powder body that obtains simultaneously is stirred continuously, and makes pre- slurry；
3. the zirconia ball 1200kg of diameter 2mm, the zirconia ball 800kg of diameter 4mm, diameter are placed with vertical mixing tank
The zirconia ball 700kg of 6mm, progressively pumps into stepThe pre- slurry of system and simultaneously by slow-to-fast turn on agitator, in 1200r/
2h is stirred under min mixing speeds；
4. the mixture after agitation grinding is filtered by the mesh of space 80, the agitated medium for leaching（It is reusable after cleaning）With it is thick
7.9 tons of the calcium carbonate slurry that water content is 30% is obtained after particulate matter, takes centrifuge dehydration to be concentrated into the calcium carbonate slurry aqueous
Measure as 23%, flow velocity 12m is sprayed into the speed of hexagonal angle 1100kg/h3Atomization is carried out in 350 DEG C of air-flows of/s and moment is evaporated,
Obtain the reunion powder body of about 5.4 tons of water content 0.9%；
5. reunion dry powder depolymerization 1min in by the high speed depolymerizer that infrared radiation device steady temperature is 135 DEG C, obtains aqueous
The powder body for 0.18% is measured, while adding chitosan solution（Shitosan accounts for the 5% of dry powder gross weight）, 23kg stearic acid is added afterwards
Zinc and 23kg stearic acid are fully reacted, and obtain 5.3 tons of ventilated membrane Chitosan-coated ground calcium carbonate antibacterial filler；
6. ventilated membrane Chitosan-coated ground calcium carbonate antibacterial filler is collected in homogenizing 3min in all mixing tank, temperature by air-flow
Being down to room temperature carries out quantitative package.
The present embodiment gained ventilated membrane is as follows with Chitosan-coated ground calcium carbonate antibacterial filler performance：Particle diameter：D502.8μ
M, D975.6 μm, diameter is less than 2 μm of particulate accumulation contents 72%；Whiteness 92；Oil factor 31.6g/100g；Sphericity 1.4；Specific surface
Product 54m2/g；Particle diameter distribution 1.5, with excellent antibacterial characteristics.
Embodiment 3
The marble Ore of selected calcium carbonate content >=99%, is broken for being put in vertical mill after the fritter of diameter 8mm（Main frame
Rotating speed 300r/min, rotation speed of fan 3000r/min）D is obtained in dust-precipitator50For 40 μm of marble powder；
4.5 tons of pure water is taken, sodium lignin sulfonate 40kg and polycarboxylic acids sodium 80kg mix homogeneously in premixing tank is added, by
Gradually add 6 tons of stepsThe powder body that obtains simultaneously is stirred continuously, and makes pre- slurry；
3. the corundum microsphere 1200kg of diameter 1.2mm, the corundum microsphere 800kg of diameter 3.4mm are placed with vertical mixing tank, directly
The corundum microsphere 1000kg of the corundum microsphere 700kg of footpath 5mm, diameter 8mm, progressively pumps into stepThe pre- slurry of system and simultaneously by
Slow-to-fast turn on agitator, under 2500 r/min mixing speeds 1.2h is stirred；
4. the mixture after agitation grinding is filtered by the mesh of space 80, the agitated medium for leaching（It is reusable after cleaning）With it is thick
The calcium carbonate slurry that water content is 38% is obtained after particulate matter, takes centrifuge dehydration to be concentrated into water content the calcium carbonate slurry to be
23%, spray into flow velocity 18m with 90 ° of angle 850kg/h speed3Atomization is carried out in 350 DEG C of air-flows of/s and moment is evaporated, obtain about 5.9
The reunion powder body of ton water content 0.9%；
5. reunion powder body depolymerization 1min in by the high speed depolymerizer that infrared radiation device steady temperature is 135 DEG C, obtains aqueous
The powder body of amount 0.16%, while adding chitosan solution（Shitosan accounts for the 3% of dry powder gross weight）, 17kg Aluminate idols are added afterwards
Connection agent and 34kg stearic acid are fully reacted, and obtain 5.8 tons of ventilated membrane Chitosan-coated ground calcium carbonate antibacterial filler；
6. ventilated membrane Chitosan-coated ground calcium carbonate antibacterial filler is collected in homogenizing 3min in all mixing tank, temperature by air-flow
Being down to room temperature carries out quantitative package.
The present embodiment gained ventilated membrane is as follows with Chitosan-coated ground calcium carbonate antibacterial filler performance：Particle diameter：D502.4μ
M, D975.4 μm, diameter is less than 2 μm of particulate accumulation contents 76%；Whiteness 92；Oil factor 33.2g/100g；Sphericity 1.4；Specific surface
Product 55m2/g；Particle diameter distribution 1.5, with preferable antibacterial characteristics.
Depolymerization equipment used is to add on the basis of many rotor-type high speed powder body depolymerizers of FW/HTS in above-described embodiment
The depolymerization equipment of infrared heating device；High-temperature atomizing flashing apparatus used is to set in peak force drying complete apparatus company QGS5 types
The atomization flash-evaporation equipment of band customized spraying adjusting apparatus on the basis of standby；But it is actual when preparing, it is not limited to the model, should
The equipment of type, other heat drying modes and high-speed stirred machinery change with batch (-type) surface modifying machine and other continuous way surfaces
The equipment such as property machine are equally applicable to the physics of relevant components or/and chemically composited and surface modification in functional stuffing of the present invention.
The ventilated membrane that now embodiment 2 is prepared Chitosan-coated ground calcium carbonate antibacterial filler and existing carbonic acid
Ventilated membrane prepared by calcium powder body carries out Performance comparision, see the table below 1：
Table 1
As can be seen from Table 1, the ventilated membrane that filler of the present invention is prepared is in air penetrability, needle pore defect, tensile strength, gloss
Several aspects such as degree are all substantially better than the ventilated membrane that existing calcium carbonate powder is prepared.
The ventilated membrane for now preparing embodiment 2 and embodiment 3 with Chitosan-coated ground calcium carbonate antibacterial filler and
The calcium carbonate powder of uncoated shitosan carries out bacteriostasis rate contrast experiment, and its results of property is as shown in figure 1, when the content of shitosan
For 0wt% when, that is, being added without shitosan carries out antibacterial experiment, and experimental result shows, antibacterial ring size does not occur, illustrates Paris white
Body itself is that do not possess antibacterial effect.When the content for adding shitosan is 3wt%, as illustrated, occurring in that significantly antibacterial
Ring, illustrates that Chitosan-coated heavy calcium carbonate filling has preferable anti-microbial property, while the Chitosan-coated can also be illustrated
The method of calcium carbonate powder is largely effective and feasible.When the content of shitosan is 5wt%, it is relative to chitosan content
3wt%, the anchor ring product of antibacterial ring size is significantly increased, and illustrates that the fungistatic effect that chitosan content is 5wt% is optimal.
To sum up, it can be seen that ventilated membrane Chitosan-coated ground calcium carbonate antibacterial filler energy prepared by the inventive method
The preferable ventilated membrane of enough processabilities, to prepare ventilated membrane a kind of preferably selection is provided.
Claims (10)
1. a kind of ventilated membrane preparation method of Chitosan-coated ground calcium carbonate antibacterial filler：Comprise the following steps：
It is a, broken：By the marble powder that the marble of calcium carbonate content >=99% is 40~70 μm of diameter；
B, homogenizing, grinding：According to weight than the ︰ 0.001~0.1 of Dali stone powder ︰ water ︰ high molecular surfactant=1 ︰ 0.2~1.5
Three is mixed, alumina ball, corundum ball or zirconium oxide that a diameter of 1~20mm accounts for three's gross weight 30~55% is added
Any one in ball, by the way of agitation grinding, mixing time be 1~5h, mixing speed be 500~6000r/min, 60
~200 mesh are filtrated to get calcium carbonate slurry；It is little that the calcium carbonate slurry dehydration that 60~200 mesh are filtrated to get is concentrated into water content
In 25%, then flow velocity is passed through as 5~60m with the speed of 400~1800kg/h3/ s, temperature is to be atomized in 300~450 DEG C of air-flow
Flash distillation to water content is not more than 1%；
It is c, modified：Reunion powder body is dismissed, and drying to water content is not more than 0.2%, addition is accounted for and is dried powder body gross weight 1%~5%
Chitosan solution, adds afterwards the activator for accounting for dry powder gross weight 0.5~2%, and in 110~140 DEG C of fully reactions, cooling is mixed
It is even, packaging.
2. a kind of ventilated membrane according to claim 1 preparation method of Chitosan-coated ground calcium carbonate antibacterial filler,
It is characterized in that：In step b, described high molecular surfactant be sodium alginate, sodium carboxymethyl cellulose, polyphosphate sodium,
Polyacrylamide, polycarboxylic acids sodium, sodium polyacrylate, sodium lignin sulfonate, Polyethylene Glycol, polypropylene glycol, polyvinyl alcohol, polyethylene
At least one in ketopyrrolidine, TH-904 dispersants or calcium lignosulfonate.
3. a kind of ventilated membrane according to claim 2 preparation method of Chitosan-coated ground calcium carbonate antibacterial filler,
It is characterized in that：Described high molecular surfactant is polyphosphate sodium by weight and the mixing gained of 1 ︰ of sodium polyacrylate 1,
Sodium lignin sulfonate and the mixing gained of 1 ︰ of polycarboxylic acids sodium 2, TH-904 dispersants and the mixing of 1 ︰ of calcium lignosulfonate 2 gained or poly- carboxylic
Any one in sour sodium and the mixing gained of 2 ︰ of sodium polyacrylate 1.
4. a kind of ventilated membrane according to claim 1 preparation method of Chitosan-coated ground calcium carbonate antibacterial filler,
It is characterized in that：In step c, the chitosan solution is water in mass ratio：Glacial acetic acid：The ︰ 0.01~0.05 of shitosan=1 ︰ 0.03
Mix homogeneously gained.
5. a kind of ventilated membrane according to claim 4 preparation method of Chitosan-coated ground calcium carbonate antibacterial filler,
It is characterized in that：The chitosan solution forms atomized liquid by atomising device, and is uniformly wrapped on heavy in the form of spraying
Calcium carbonate surface.
6. a kind of ventilated membrane according to claim 1 preparation method of Chitosan-coated ground calcium carbonate antibacterial filler,
It is characterized in that：In step c, described activator is stearic acid, humic acid, Oleic acid, silicol, calcium stearate, stearic acid
Zinc, enuatrol, sodium palmitate, palmitic acid calcium, dodecyl sodium sulfate, ethylene bis stearic acid amide, stearic acid monoglycerides, second two
Amine, aqueous epoxy resins, epoxy soybean oil, Toluene-2,4-diisocyanate, 4- diisocyanate, 6- methylene polyisocyanates, Aluminate are coupled
At least one in agent, titanate coupling agent or silane coupler.
7. a kind of ventilated membrane according to claim 6 preparation method of Chitosan-coated ground calcium carbonate antibacterial filler,
It is characterized in that：Described activator is stearic acid by weight and the mixing gained of 1 ︰ of zinc stearate 1, calcium stearate and ethylene
The mixing gained of 1 ︰ of double stearic amides 1, Oleic acid and the mixing gained of 1 ︰ of stearic acid 1, ethylenediamine and the ︰ 1 of 6- methylene polyisocyanates 1
Mixing gained or aluminate coupling agent and stearic acid are mixed any one in gained by 1 ︰ 2.
8. the Chitosan-coated ground calcium carbonate antibacterial filler of a kind of ventilated membrane according to any one of claim 1~7
Preparation method, it is characterised in that：In step a, also including the additive for accounting for marble weight 0.2~0.8%, described additive
For at least one in glycerol or ethylene glycol.
9. the system of Chitosan-coated ground calcium carbonate antibacterial filler of a kind of ventilated membrane by described in any one of claim 1~8
The ventilated membrane heavy calcium carbonate filling that Preparation Method is prepared.
10. by a kind of preparation method system of Chitosan-coated ground calcium carbonate antibacterial filler of the ventilated membrane described in claim 9
The standby breathable films dedicated parent material for obtaining or breathable films PP Pipe Compound.
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| CN107602921A (en) * | 2017-09-08 | 2018-01-19 | 贺州钟山县双文碳酸钙新材料有限公司 | A kind of modified calcium carbonate and its production technology applied to plastics |
| CN109825111A (en) * | 2019-03-29 | 2019-05-31 | 桂林理工大学 | A kind of free from vacuum dehydrating can be used to the pearl filler of production silane modified polyether seal glue |
| CN111705543A (en) * | 2020-05-28 | 2020-09-25 | 仙鹤股份有限公司 | Preparation method of high-whiteness high-strength carbonless copy paper base paper |
| CN112852048A (en) * | 2021-01-12 | 2021-05-28 | 中广核俊尔(浙江)新材料有限公司 | PE (polyethylene) breathable film material as well as preparation method and application thereof |
| CN112962356A (en) * | 2021-01-26 | 2021-06-15 | 湖南工业大学 | Waterproof paper pulp molding material with high compressive strength and preparation method thereof |
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| CN111705543A (en) * | 2020-05-28 | 2020-09-25 | 仙鹤股份有限公司 | Preparation method of high-whiteness high-strength carbonless copy paper base paper |
| CN112852048A (en) * | 2021-01-12 | 2021-05-28 | 中广核俊尔(浙江)新材料有限公司 | PE (polyethylene) breathable film material as well as preparation method and application thereof |
| CN112962356A (en) * | 2021-01-26 | 2021-06-15 | 湖南工业大学 | Waterproof paper pulp molding material with high compressive strength and preparation method thereof |
| CN114434922A (en) * | 2022-03-01 | 2022-05-06 | 浙江盛纺纳米材料科技有限公司 | Laminating non-woven fabric and preparation method thereof |
| CN114434922B (en) * | 2022-03-01 | 2023-02-28 | 浙江盛纺纳米材料科技有限公司 | Laminating non-woven fabric and preparation method thereof |
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