A kind of ventilated membrane heavy calcium carbonate filling and preparation method thereof
Technical field
The invention belongs to nonmetallic mineral deep processing and utilization, composite and field of functional materials are and in particular to one kind is saturating
Air film heavy calcium carbonate filling and preparation method thereof.
Background technology
With the raising of social progress and people's living standard, in daily life, medical treatment, special industrial protection field, one
The usage amount of secondary property product and range progressively expand, and have reached 30,000,000,000 in the sales volume of China's disposable product in 2013
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 in a large number using plastic film material, traditional plastic sheeting
It is air-locked, the breathability 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 obtain that there is answering of micropore through longitudinal direction or biaxial tension
Closing thin film is the modal at present method improving plastic sheeting breathability, 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 suitable external force effect
Face is peeled off, and polymer extends and forms the micropore running through.The pore structure mutually running through allows small molecule gaseous material through (as water
Steam, air etc.), but liquid cannot pass through such micropore due to surface tension effects, be consequently formed and have
Gas fluid-tight barriers function thin film.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 preparing laminated film.Based on this, to laminated film system
Used in standby, filler just proposes at a relatively high prescription, common filler on the market, such as ground calcium carbonate, Pulvis Talci, weight
Spar etc. all can not meet the prescription of ventilated membrane.
Manufacture ventilated membrane with traditional heavy calcium carbonate filling to have the problem that
1st, because particle diameter distribution extensively makes the composite membrane low intensity of preparation, do not reach use requirement, granule has obvious rib
Angle, the composite membrane of preparation can stimulate skin;
2nd, the composite membrane of preparation can form a large amount of pinprick defects during stretching pore-forming, and pinprick leads to liquid also can pass through
Thin film;
The air penetrability of the ventilated membrane the 3rd, made is unstable, forms the air-locked region in local;
4th, filler moves to film surface under stress, makes one layer of tear-away powder body of ventilated membrane surface attachment;
5th, the grinding aid that filler uses does not account for toxic it is impossible to reach the hygienic requirements of ventilated membrane;
6th, filler disperse in composite membrane uneven, cause ventilated membrane coloured dyeing speckle etc. impact quality.
Inventor is directed to the deficiency of current heavy calcium carbonate powder filler, and particularly traditional triple superphosphate is used in ventilated membrane production
Problem and defect, provide a kind of brand-new ground calcium carbonate functional stuffing to produce preparation scheme.
Content of the invention
First technical problem to be solved by this invention is to provide a kind of preparation of ventilated membrane heavy calcium carbonate filling
Method.The method comprises the following steps:
A, by the marble of calcium carbonate content >=99% be 40~70 μm of diameter marble powder;
B, according to weight than marble powder water high molecular surfactant=1 0.2~1.5 0.001~0.1 by three
Mix, add in alumina ball, corundum ball or the zirconia ball that a diameter of 1~20mm accounts for three's gross weight 30~55%
Any one, grind, and 60~200 mesh are filtrated to get calcium carbonate slurry;
C, calcium carbonate slurry is dehydrated it is not more than 1% to water content, obtain reunion powder body;
D, dismiss reunion powder body, and be dried and be not more than 0.2% to water content, add account for be dried after powder gross weight 0.5~
3% activator, fully reacts at 110~140 DEG C, and cooling mixes, packs.
Specifically, in above-mentioned preparation method step b, described high molecular surfactant is sodium alginate, carboxymethyl is fine
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 dispersant or calcium lignosulfonate.
Preferably, in above-mentioned preparation method step b, described high molecular surfactant is polyphosphate sodium by weight
With sodium polyacrylate 11 mixing gained, sodium lignin sulfonate and polycarboxylic acids sodium 12 mixing gained, th-904 dispersant and wooden
Plain sulfoacid calcium 12 mixes any one in gained or polycarboxylic acids sodium and sodium polyacrylate 21 mixing gained.
Preferably, in above-mentioned preparation method step b, by the way of stirring, mixing time is 1~5h for described grinding,
Mixing speed is 500~6000r/min.
Specifically, in above-mentioned preparation method step d, described activator is stearic acid, humic acid, Oleic acid, silicol,
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, the 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 d, described activator is stearic acid and zinc stearate 1 by weight
1 mixing gained, calcium stearate and ethylene bis stearic acid amide 11 mixing gained, Oleic acid and stearic acid 11 mixing gained, second two
Amine and 6- methylene polyisocyanates 11 mix gained or aluminate coupling agent and stearic acid by any in 12 mixing gained
A kind of.
Specifically, in above-mentioned preparation method step c, described dehydration to water content is not more than 1% and adopts following steps real
Existing: the calcium carbonate slurry dehydration that 60~200 mesh are filtrated to get is concentrated into water content and is not more than 25%, then with 400~1800kg/
It is 5~60m that the speed of h is passed through flow velocity3/ s temperature is that in 300~450 DEG C of air-flow, atomization flash-evaporation is not more than 1% to water content.
Specifically, in above-mentioned preparation method step a, also include accounting for the additive of marble weight 0.2~0.8%, described
Additive be at least one in glycerol or ethylene glycol.
Second technical problem to be solved by this invention is to provide by the system of above-mentioned ventilated membrane heavy calcium carbonate filling
The ventilated membrane heavy calcium carbonate filling that Preparation Method prepares.
Specifically, above-mentioned ventilated membrane heavy calcium carbonate filling, particle diameter: d50=0.5~5 μm, d97≤ 10 μm, diameter is little
In 2 μm of particulate accumulation content >=45%;Whiteness >=82;Oil factor 15~60g/100g;Sphericity 1.2~1.9;Specific surface area >=
35m2/g;Particle diameter distribution≤1.7.
3rd technical problem to be solved by this invention is to provide above-mentioned ventilated membrane heavy calcium carbonate filling to be prepared into
The breathable films dedicated parent material arriving or breathable films PP Pipe Compound.
Product of the present invention has the advantages that
1st, the sphericity of calcium carbonate powder of the present invention very well, does not have corner angle, the composite membrane of preparation will not stimulate skin;
2nd, diameter of particle narrowly distributing of the present invention, when preparing ventilated membrane, will not form the uneven, needle pore defect of dispersion;
3rd, the present invention is raw materials used harmless, and the ventilated membrane prepared can be with Long Term Contact human body;
4th, powder body of the present invention be used for ventilated membrane in, in use will not migration precipitation, will not fall off.
Specific embodiment
A kind of preparation method of ventilated membrane heavy calcium carbonate filling, comprises the following steps:
A, by the marble of selected calcium carbonate content >=99% through multiple stage crushing to a diameter of 3~10mm, meticulous easily
Introduce other impurities, excessive to easily cause grinding efficiency low;Again its dry state is ground to diameter at 40~75 μm, obtains marble
Powder;
B, in order to improve grinding efficiency and drying efficiency, add high molecular surfactant, by weight, marble powder
Three is mixed by water high molecular surfactant=1 0.2~1.5 0.001~0.1;In order to by ventilated membrane calcium carbonate for special use powder
Body grinds to form required index and saves milling time, adds a diameter of 1~20mm and accounts for three's gross weight 30~55%
Any one in alumina ball, corundum ball or zirconia ball, stirs 1~5h, and mixing speed is 500~6000r/min, and 60
~200 mesh drainage screens carry out being filtrated to get calcium carbonate slurry;Described high molecular surfactant is sodium alginate, carboxymethyl is fine
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 dispersant or calcium lignosulfonate;
C, by calcium carbonate slurry be dehydrated concentrate, make the water content of calcium carbonate slurry be not more than 25%, with 400~1800kg/h
Speed be passed through flow velocity be 5~60m3/ s temperature is that in 300~450 DEG C of air-flow, atomization flash-evaporation is not more than 1% to water content;
D, dismission reunion powder body, and it is not more than 0.2% with infrared drying to water content, addition accounts for powder gross weight after being dried
0.5~3% activator fully reacts in 110~140 DEG C, cooling, mixes, packs;Described activator be stearic acid,
Humic acid, Oleic acid, silicol, calcium stearate, zinc stearate, enuatrol, sodium palmitate, palmitic acid calcium, dodecyl sodium sulfonate
Sodium, ethylene bis stearic acid amide, stearic acid monoglycerides, ethylenediamine, aqueous epoxy resins, epoxy soybean oil, Toluene-2,4-diisocyanate, 4- bis- is different
At least one in cyanate, 6- methylene polyisocyanates, aluminate coupling agent, titanate coupling agent or silane coupler.
Preferably, in above-mentioned preparation method step b, described high molecular surfactant is polyphosphate sodium by weight
With sodium polyacrylate 11 mixing gained, sodium lignin sulfonate and polycarboxylic acids sodium 12 mixing gained, th-904 dispersant and wooden
Plain sulfoacid calcium 12 mixes any one in gained or polycarboxylic acids sodium and sodium polyacrylate 21 mixing gained.
Preferably, in above-mentioned preparation method step d, described activator is stearic acid and zinc stearate 1 by weight
1 mixing gained, calcium stearate and ethylene bis stearic acid amide 11 mixing gained, Oleic acid and stearic acid 11 mixing gained, second two
Amine and 6- methylene polyisocyanates 11 mix gained or aluminate coupling agent and stearic acid by any in 12 mixing gained
A kind of.
Preferably, in above-mentioned preparation method step a, also include accounting for the additive of marble weight 0.2~0.8%, described
Additive be at least one in glycerol or ethylene glycol.
Filled out by the ventilated membrane ground calcium carbonate that the preparation method of above-mentioned ventilated membrane heavy calcium carbonate filling prepares
Material.
Specifically, above-mentioned ventilated membrane heavy calcium carbonate filling, particle diameter: d50=0.5~5 μm, d97≤ 10 μm, diameter is little
In 2 μm of particulate accumulation content >=45%;Whiteness >=82;Oil factor 15~60g/100g;Sphericity 1.2~1.9;Specific surface area >=
35m2/g;Particle diameter distribution≤1.7.
Breathable films dedicated parent material or breathable films PP Pipe Compound that above-mentioned ventilated membrane heavy calcium carbonate filling prepares.
D in product index of the present invention50Represent and press quantity statistics mean diameter;d97Represent the particle size range of 97% powder body;
Oil factor represents allows the minimum quality of the agglomerating required butyl phthalate of 100g powder body;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 of statistics and the mean diameter by statistic of attribute by weight.
Due to traditional Calcium Carbonate be used for ventilated membrane problem many, cause the reason these be: the particle diameter of traditional calcium carbonate powder
Greatly, sphericity is low, particle diameter distribution is too wide, traditional organic-treating of calcium carbonate surface does not reach wanting of composite conjugation
Ask, calcium carbonate powder secondary agglomeration is serious etc..
The present inventor is after many experiments find using high molecular surfactant and zirconium oxide microballon, conventional
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 can overcome above-mentioned problem to the filler preparing after powder surface organic-treating, 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 finds to add in the feed high molecular surfactant, both
Can meet and be dried and grinding efficiency, high molecular surfactant can be attached to powder surface again, reduce reunion when being dried
Degree, thus reached 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 effect and the 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 adopts 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, forming chemical bond, Organic substance being fixed on powder surface, thus carrying
The compatibility between high powder body and polymer, when preparing ventilated membrane, is conducive to disperseing and improve ventilative film strength.
Embodiment 1
1. the marble Ore of selected calcium carbonate content >=99%, puts in ring barreling after being broken for the fritter of diameter 3mm
(engine speed 1100r/min, rotation speed of fan 4000r/min) obtains d in dust-precipitator50For 50 μm of marble powder;
2. take 4 tons of pure water, add polycarboxylic acids sodium (commercially available ROHM AND HAAS 9400) 100kg mix homogeneously in premixing tank,
It is gradually added into the marble powder that 1. 6 tons of steps obtain and is stirred continuously, make pre- slurry;
3. it is placed with diameter 1.2mm zirconia ball 800kg, diameter 2.2mm zirconia ball 1200kg in vertical mixing tank, directly
Footpath 3.8mm zirconia ball 2000kg, progressively pumps into the pre- slurry that 2. step make and simultaneously by slow-to-fast turn on agitator,
1.5h is stirred under 1800r/min mixing speed;
4. the mixture after stirring passes through 100 mesh and filters, and leaches agitated medium (reusable after cleaning) and coarse granule
Obtain about 9.3 tons of the calcium carbonate slurry that water content is 35% after thing, take centrifuge dehydration to be concentrated into this calcium carbonate slurry aqueous
Measure as 23%, flow velocity 15m is sprayed into the speed of 45° angle 650kg/h3Carry out atomization in 350 DEG C of air-flows of/s and moment is evaporated, obtain
Reunion powder body to about 5.9 tons of water content 0.8%;
5. reunion powder body depolymerization 1min in the high speed depolymerizer being 135 DEG C by infrared radiation device steady temperature, obtains
Water content is 0.16% powder body, and the silane coupler (commercially available kh550) being simultaneously introduced 50kg is fully reacted, and is breathed freely
5.8 tons of film calcium carbonate for special use powder body;
6. ventilated membrane calcium carbonate for special use powder body is collected in homogenizing 3min in all mixing tank by air-flow, and temperature is down to room temperature and is carried out
Quantitative package.
The present embodiment gained ventilated membrane calcium carbonate for special use powder characteristic is as follows: particle diameter: d50=2.2 μm,d97=5.8 μm, directly
Footpath is less than 2 μm of particulate accumulation contents 78%;Whiteness 91;Oil factor 32g/100g;Sphericity 1.4;Specific surface area 55m2/g;Particle diameter
Distribution 1.5.
Embodiment 2
1. the marble Ore of selected calcium carbonate content >=99%, puts in ball mill after being broken for the fritter of diameter 8mm
(engine speed 600r/min, rotation speed of fan 2000r/min) obtains d in dust-precipitator50For 40 μm of marble powder;
2. take 2.5 tons of pure water, add sodium polyacrylate (commercially available molecular weight is more than 10,000) 120kg to mix in premixing tank
Uniformly, it is gradually added into the powder body that 1. 5.5 tons of steps obtain and is stirred continuously, make pre- slurry;
3. it is placed with the zirconia ball 1200kg of diameter 2mm, the zirconia ball 800kg of diameter 4mm in vertical mixing tank, directly
The zirconia ball 700kg of footpath 6mm, progressively pumps into the pre- slurry that 2. step make and simultaneously by slow-to-fast turn on agitator,
2h is stirred under 1200r/min mixing speed;
4. the mixture after agitation grinding passes through space 80 mesh filtration, the agitated medium (reusable after cleaning) leaching
With obtain 7.9 tons of the calcium carbonate slurry that water content is 30% after coarseparticulate, this calcium carbonate slurry is taken centrifuge dehydration concentrate
It is 23% to water content, flow velocity 12m is sprayed into the speed of hexagonal angle 1100kg/h3It is atomized and wink in 350 DEG C of air-flows of/s
Between be evaporated, obtain the reunion powder body of about 5.4 tons of water content 0.9%;
5. reunion dry powder depolymerization 1min in the high speed depolymerizer being 135 DEG C by infrared radiation device steady temperature, obtains
Water content is 0.18% powder body, is simultaneously introduced 23kg zinc stearate and 23kg stearic acid is fully reacted, obtain ventilated membrane
5.3 tons of calcium carbonate for special use powder body;
6. ventilated membrane calcium carbonate for special use powder body is collected in homogenizing 3min in all mixing tank by air-flow, and temperature is down to room temperature and is carried out
Quantitative package.
The present embodiment gained ventilated membrane calcium carbonate for special use powder characteristic is as follows: particle diameter: d502.8 μm, d975.6 μm, diameter is little
In 2 μm of particulate accumulation contents 72%;Whiteness 92;Oil factor 31.6g/100g;Sphericity 1.4;Specific surface area 54m2/g;Particle diameter divides
Cloth 1.5.
Embodiment 3
1. the marble Ore of selected calcium carbonate content >=99%, puts in vertical mill after being broken for the fritter of diameter 8mm
(engine speed 300r/min, rotation speed of fan 3000r/min) obtains d in dust-precipitator50For 40 μm of marble powder;
2. take 4.5 tons of pure water, add sodium lignin sulfonate 40kg and polycarboxylic acids sodium 80kg mix homogeneously in premixing tank,
It is gradually added into the powder body that 1. 6 tons of steps obtain and is stirred continuously, make pre- slurry;
3. it is placed with the corundum microsphere 1200kg of diameter 1.2mm, the corundum microsphere of diameter 3.4mm in vertical mixing tank
The corundum microsphere 1000kg of the corundum microsphere 700kg of 800kg, diameter 5mm, diameter 8mm, progressively pumps into the pre- slurry that 2. step is made
And simultaneously by slow-to-fast turn on agitator, stir 1.2h under 2500r/min mixing speed;
4. the mixture after agitation grinding passes through space 80 mesh filtration, the agitated medium (reusable after cleaning) leaching
With obtain the calcium carbonate slurry that water content is 38% after coarseparticulate, take centrifuge dehydration to be concentrated into this calcium carbonate slurry aqueous
Measure as 23%, spray into flow velocity 18m with 90 ° of angle 850kg/h speed3Carry out atomization in 350 DEG C of air-flows of/s and moment is evaporated, obtain
The reunion powder body of about 5.9 tons of water content 0.9%;
5. reunion powder body depolymerization 1min in the high speed depolymerizer being 135 DEG C by infrared radiation device steady temperature, obtains
The powder body of water content 0.16%, is simultaneously introduced 17kg aluminate coupling agent and 34kg stearic acid is fully reacted, and is breathed freely
5.8 tons of film calcium carbonate for special use powder body;
6. ventilated membrane calcium carbonate for special use powder body is collected in homogenizing 3min in all mixing tank by air-flow, and temperature is down to room temperature and is carried out
Quantitative package.
The present embodiment gained ventilated membrane calcium carbonate for special use powder characteristic is as follows: particle diameter: d502.4 μm, d975.4 μm, diameter is little
In 2 μm of particulate accumulation contents 76%;Whiteness 92;Oil factor 33.2g/100g;Sphericity 1.4;Specific surface area 55m2/g;Particle diameter divides
Cloth 1.5.
In above-described embodiment, depolymerization equipment used is to add on the basis of fw/hts many rotor-types high speed powder body depolymerizer
The depolymerization equipment of infrared heating device;High-temperature atomizing flashing apparatus used is to set in peak force drying complete apparatus company qgs5 type
The atomization flash-evaporation equipment of band customized spraying adjusting apparatus on the basis of standby;But during actual preparation it is not limited to this model, should
The equipment of type, other heat drying modes and high-speed stirred machinery are changed with batch (-type) surface modification 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.
Now the ventilated membrane heavy calcium carbonate filling that embodiment 2 prepares is used for preparing ventilated membrane and existing carbonic acid
The ventilated membrane of calcium powder body preparation carries out Performance comparision, see table 1:
Table 1
As can be seen from Table 1, the ventilated membrane that filler of the present invention prepares air penetrability, needle pore defect, tensile strength,
Several aspect such as glossiness is all substantially better than the ventilated membrane that existing calcium carbonate powder prepares.So, the inventive method system
Standby ventilated membrane heavy calcium carbonate filling can the preferable ventilated membrane of processability, for prepare ventilated membrane provide a kind of more preferably
Selection.